The Effects of Hydrophobicity and Textural Properties on Hexamethyldisiloxane Adsorption in Reduced Graphene Oxide Aerogels

To expand the applications of graphene-based materials to biogas purification, a series of reduced graphene oxide aerogels (rGOAs) were prepared from industrial grade graphene oxide using a simple hydrothermal method. The influences of the hydrothermal preparation temperature on the textural properties, hydrophobicity and physisorption behavior of the rGOAs were investigated using a range of physical and spectroscopic techniques. The results showed that the rGOAs had a macro-porous three-dimensional network structure. Raising the hydrothermal treatment temperature reduced the number of oxygen-containing groups, whereas the specific surface area (S_BET), micropore volume (V_micro) and water contact angle values of the rGOAs all increased. The dynamic adsorption properties of the rGOAs towards hexamethyldisiloxane (L2) increased with increasing hydrothermal treatment temperature and the breakthrough adsorption capacity showed a significant linear association with S_BET, V_micro and contact angle. There was a significant negative association between the breakthrough time and inlet concentration of L2, and the relationship could be reliably predicted with a simple empirical formula. L2 adsorption also increased with decreasing bed temperature. Saturated rGOAs were readily regenerated by a brief heat-treatment at 100 °C. This study has demonstrated the potential of novel rGOA for applications using adsorbents to remove siloxanes from biogas.     

Design,Synthesis and Anticancer Activity of a New Series of N-aryl-N′-[4-(pyridin-2-ylmethoxy)benzyl]urea Derivatives

The development of cancer treatments requires continuous exploration and improvement, in which the discovery of new drugs for the treatment of cancer is still an important pathway. In this study, based on the molecular hybridization strategy, a new structural framework with an N-aryl-N’-arylmethylurea scaffold was designed, and 16 new target compounds were synthesized and evaluated for their antiproliferative activities against four different cancer cell lines A549, MCF7, HCT116, PC3, and human liver normal cell line HL7702. The results have shown seven compounds with 1-methylpiperidin-4-yl groups having excellent activities against all four cancer cell lines, and they exhibited scarcely any activities against HL7702. Among them, compound 9b and 9d showed greatly excellent activity against the four kinds of cells, and the IC₅₀ for MCF7 and PC3 cell lines were even less than 3 μM.     

The Effect of Oleic Acid Emulsification using SPE on Fluorite and Dolomite Flotation**

Collector OA, oleic acid, is widely used industrially for fluorite flotation. Low selectivity, dispersibility and collecting capability of the OA collector are always observed. In this study, compared with flotation of dolomite, a collector mixture of OA and SPE (styrylphenol polyoxyethylene ether) demonstrated significantly better performances for the fluorite. An optimal mass ratio 4 : 1 OA : SPE was found, and the recovery of fluorite was increased from over 85 % to more than 94 % compared with pure OA. Furthermore, the dosage of the collector agent was reduced from 50 mg mL⁻¹ to 20 mg mL⁻¹, which did not negatively impact the recovery of dolomite. The results from the contact angle tests indicated that SPE selectively increased the surface hydrophobicity of fluorite but had little effect on dolomite. Besides, zeta potential measurements and IR analyses revealed that the addition of SPE led to strong chemical adsorption on the surface of fluorite, resulting in a significant difference in the flotation performances of the two minerals. Therefore, SPE-emulsified OA is corroborated to prompt more selectivity and collecting capability on flotation of fluorite over dolomite.     

Simultaneous Determination of 1-Methyltryptophan and Indoleamine 2,3-Dioxygenase Biomakers of Tryptophan and Kynurenine in Mice Tumors by HPLC–MS/MS

Indoleamine 2,3-dioxygenase (IDO), an immune checkpoint protein, can cause the depletion of tryptophan (Trp) and accumulation of its metabolite of kynurenine (Kyn) in cancer cells, and generates the immunosuppressive microenvironment that supports tumor cell growth. A novel immunoregulatory prodrug micelle based on polyethylene glycol-derivatized an IDO-selective inhibitor of 1-methyltryptophan (1-MT), PEG-Fmoc-1-MT, was developed for inhibiting the IDO activity of the conversion of Trp to Kyn in tumor microenvironments. To investigate the 1-MT distribution and Trp/Kyn ratios in mice tumors with PEG-Fmoc-1-MT prodrug micelles treatment, a HPLC–MS/MS method for simultaneous determination of 1-MT and IDO biomakers of Trp and Kyn in mouse tumors was developed and validated. Triple-quadrupole mass spectrometry with positive electrospray ionization as source ionization in multiple reaction monitoring at m/z 219.0?→?160.1, 205.0?→?118.2, 209.0?→?146.1 and 249.3?→?148.3 was used for determination of 1-MT, Trp, Kyn and matrine (internal standard). The method demonstrated good linearity at the concentrations ranging from 10 to 10,000 ng/mL and lower limits of quantitation of 1 ng/mL for 1-MT, Trp and Kyn, respectively. The validated method was successfully applied to 1-MT tumor biodistribution and Trp/Kyn ratio studies in 4T1 tumor bearing mice i.v. with PEG-Fmoc-1-MT prodrug micelles. The mice tumors with PEG-Fmoc-1-MT prodrug micelles treatment exhibited higher 1-MT accumulation and lower Trp/Kyn ratio, in comparison with those of mice with 1-MT solution treatment. The developed PEG-Fmoc-1-MT prodrug micelles could be a promising IDO immunoregulatory prodrug micelles for cancer immunotherapy.

     

Paternal genetic structure of Kyrgyz ethnic group in China revealed by high-resolution Y-chromosome STRs and SNPs

Kyrgyz ethnic group is one of the nomads in China, with the majority in Xinjiang and a small part of them living in Heilongjiang province. Historically, they have went through five migrations westward due to the wars. The name “Kyrgyz” means 40 tribes, originating from the primary groups of Kyrgyz. However, it is a largely understudied population, especially from the Y chromosome. In this study, we used a previously validated high-resolution Y-chromosome single nucleotide polymorphisms (Y-SNPs) and short tandem repeats (Y-STRs) system to study Kyrgyz ethnic group. A total of 314 male samples of Kyrgyz ethnic group were genotyped by 173 Y-SNPs and 27 Y-STRs. After data analysis, the results unveiled that Kyrgyz ethnic group was a population with high percentage of both haplogroup C2a1a3a1d∼-F10091 (91/134) and R1a1a1b2a2-Z2124 (109/134), which has never been reported. This implied that Kyrgyz ethnic group might have gone through bottleneck effects twice, with these two main lineages left. Mismatch analysis indicated that the biggest mismatch number in haplogroup C2a1a3a1d∼-F10091 was 10, while that of haplogroup R1a1a1b2a2-Z2124 was 20. This huge difference reflected the different substructure in two lineages, suggesting that haplogroup C2a1a3a1d∼-F10091 might have the least admixture compared to the other two lineages. After admixture modelling with other datasets, the conclusion could be drawn that Kyrgyz ethnic group had great genetic affinity with Punjabi from Lahore, Pakistan, which supported that Kyrgyz ethnic group in China was close to central Asian.     

BirA*-protein A fusion protein based BioEnhancer amplifies western blot immunosignal

Western blot (protein immunoblot) is a widely used analytical technique in molecular biology. Utilizing the specific recognizing primary antibody, proteins immobilized on various matrix are investigated by subsequent visualization steps, for example, by the horse radish peroxidase conjugated secondary antibody incubation. Methods to improve the sensitivity in protein identification or quantification are appreciated by biochemists. Herein, we report a new strategy to amplify Western blot signals by constructing a probe with proximal labeling and IgG targeting abilities. The R118G mutation attenuated the biotin-AMP binding affinity of the bacterial biotin ligase BirA*, offering a proximity-dependent labeling ability, which could be used as a signal amplifier. We built a BirA*-protein A fusion protein (BioEnhancer) that specifically binds to IgG and adds biotin tags to its proximal amine groups, enhancing the immunosignal of target proteins. In our experiments, the BioEnhancer system amplified the immunosignal by tenfold compared to the standard western blot. Additionally, our strategy could couple with other signal enhancement methods to further increase the western blot sensitivity.     

一种检测CO32-比率荧光探针的合成及其在细胞成像中的应用

本文设计开发了一种以2,6-二甲酰基对甲苯酚为母体的新型荧光探针HMI,可用于高效识别EtOH-H₂O (8/2, v/v, HEPES 10 mM, pH =7.4)体系中的CO_3^2-。HMI在660 nm处显示发射带,加入CO_3^2-后,在600 nm的等吸收点激发时,原来在660 nm处的荧光淬灭,而以540 nm为中心的新发射带荧光显着增加,为比率型荧光探针。HMI对CO_3^2-表现出高选择性且具有较强的抗干扰能力。此外,荧光探针HMI对CO_3^2-荧光响应的检测限较低,可达到3.938×10^_-6 M。更具有意义的是,HMI探针对CO_3^2-的检测能够在实际水样中起到很好的应用,而且细胞成像研究表明,HMI可用于活体MCF-7细胞中CO_3^2-的成像。     

A De Giorgi Type Result to Divergence Degenerate Elliptic Equation with Bounded Coefficients Related To Hörmander's Vector Fields

In this paper, we consider the divergence degenerate elliptic equation with bounded coefficients constructed by Hörmander's vector fields. We prove a De Giorgi type result, i.e., the local Hölder continuity for the weak solutions to the equation by providing a De Giorgi type lemma and extending the Moser iteration to the setting here. As a consequence, the Harnack inequality of weak solutions is also given.     

Effect of Intercalated LiF on Interface Contact Characteristics of MoS2 Field Effect Transistor: A First-Principles Study

Based on the first-principles calculation, the effect of intercalated LiF on the contact characteristics of the interface between Au electrode and MoS₂ layer is studied. It is found that adding LiF film can change the contact type between metal electrode Au and MoS₂ layer from Schottky contact to ohmic contact, which is accompanied by interfacial charge transfer from LiF layer to MoS₂ layer and the downward movement of d (d_xy and d_z2) orbital of Mo atom and p (p_x and p_y) orbital of S atom to Fermi level. And the interlayer spacing between LiF layer and Au electrode has a great impact on the interface contact characteristics. The electric field effect and stress effect of interface contact of Au, LiF and MoS₂ (Au/LiF/MoS₂)is more obvious than that of interface contact of Au and MoS₂ (Au/MoS₂). Au/LiF/MoS₂ shows ohmic contact with the interlayer spacing between Au layer and LiF layer less than 3.05 Å and with the electric field less than 0.15 VÅ⁻¹, respectively, while Au/MoS₂ still shows N-type Schottky contact. These findings are helpful to control the contact resistance and have guiding significance for high performance MoS₂ field effect transistor and other electronic components.     

空心NiCo2S4纳米球助催化剂担载ZnIn2S4纳米片用于可见光催化制氢

纳米片与空心球上之间的合理界面调控是开发高效太阳能制氢光催化剂的潜在策略。在各类光催化材料中,金属硫化物由于具有相对较窄的带隙和优越的可见光响应能力而被广泛研究。ZnIn₂S₄是一种层状的三元过渡金属半导体光催化剂,其带隙可控(约2.4 eV)。在众多金属硫化物光催化剂中,ZnIn₂S₄引起了广泛兴趣。然而,单纯的ZnIn₂S₄光催化活性仍然相对较差,主要是因为光生载流子的复合率较高、迁移速率较慢。在半导体光催化剂上负载助催化剂是提升光催化剂性能的一种有效方法,因为它不仅可以加速光生电子和空穴的分离,而且还可以降低质子还原反应的活化能。作为一种三元过渡金属硫化物,NiCo₂S₄表现出较高的导电性、较低的电负性、丰富的氧化还原特性以及优越的电催化活性。这些特性表明,NiCo₂S₄可以作为光催化制氢的助催化剂,以加速电荷分离和转移。此外,NiCo₂S₄和ZnIn₂S₄都属于三元尖晶石的晶体结构,这可能有助于构建具有紧密界面接触的NiCo₂S₄/ZnIn₂S₄复合物,从而提高光催化性能。本文中,将超薄ZnIn₂S₄纳米片原位生长到非贵金属助催化剂NiCo₂S₄空心球上,形成具有强耦合界面和可见光吸收的NiCo₂S₄@ZnIn₂S₄分级空心异质结构光催化剂。最优NiCo₂S₄@ZnIn₂S₄复合样品(NiCo₂S₄含量：ca. 3.1%)的析氢速率高达78 μmol·h^-1,约是纳米片组装ZnIn₂S₄光催化剂析氢速率的9倍、约是1% (w, 质量分数)Pt/ZnIn₂S₄样品析氢速率的3倍。此外,该复合光催化剂在反应中表现出良好的稳定性。荧光和电化学测试结果表明,NiCo₂S₄空心球是一种有效的助催化剂,可促进光生载流子的分离和传输,并降低析氢反应的活化能。最后,提出了NiCo₂S₄@ZnIn₂S₄光催化析氢的可能反应机理。在NiCo₂S₄@ZnIn₂S₄复合光催化剂中,具有高导电性的NiCo₂S₄助催化剂可快速接受ZnIn₂S₄上的光生电子,用以还原质子生成氢气,而电子牺牲剂TEOA捕获光生空穴,进而完成光催化氧化还原循环。该研究有望为基于纳米片为次级结构的分级空心异质结光催化剂的设计合成及其光催化制氢研究提供一定的指导。