Spectroscopic Studies of the Modification of Crystalline Si(111) Surfaces with Covalently-Attached Alkyl Chains Using a Chlorination/Alkylation Method

A two-step procedure, involving radical-initiated chlorination of the Si surface with PCl_5 followed by reaction of the chlorinated surface with alkyl-Grignard or alkyl-lithium reagents, has been developed to functionalize crystalline (111)-oriented H-terminated Si surfaces. The surface chemistry that accompanies these reaction steps has been investigated using X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), temperature programmed desorption spectroscopy (TPDS), high-resolution electron energy loss spectroscopy (HREELS), infrared (IR) spectroscopy in both glancing transmission (TIR) and attenuated total multiple internal reflection (ATR) modes, ellipsometry, and contact angle goniometry. The XPS data show the appearance of the Cl signal after exposure to PCl_5 and show its removal, and concomitant appearance of a C 1s signal, after the alkylation step. Auger electron spectra, in combination with TPD spectroscopy, demonstrate the presence of Cl after the chlorination process and its subsequent loss after thermal desorption of Si−Cl fragments due to heating the Si surface to 1200 K. High-resolution XP spectra of the Si 2p region show a peak corresponding to Si−Cl bond formation after the chlorination step, and show the subsequent disappearance of this peak after the alkylation step. IR spectra show the loss of the perpendicularly polarized silicon monohydride (Si−H) vibration at 2083 cm^(-1) after the chlorination step, whereas HREELS data show the appearance of vibrations due to Si−Cl stretches upon chlorination of the Si surface. The HREELS data furthermore show the disappearance of the Si−Cl stretch and the appearance of a Si−C vibration at 650 cm^(-1) after alkylation of the Si surface. Ellipsometric measurements indicate that the thickness of the alkyl overlayer varies monotonically with the length of the alkyl group used in the reactant. Contact angle and IR measurements indicate that the packing of alkyl groups in the monolayers produced by this method is less dense than that found in alkylthiol monolayers on Au. As determined by XPS, the alkylated surfaces show enhanced resistance to oxidation by various wet chemical treatments, compared to the H-terminated Si surface. The two-step reaction sequence thus provides a simple approach to functionalization of (111)-oriented, H-terminated silicon surfaces using wet chemical methods

Abrupt climatic events recorded by the Ili loess during the last glaciation in Central Asia: Evidence from grain-size and minerals

The loess record of Central Asia provides an important archive of regional climate and environmental changes. In contrast to the widely investigated loess deposits in the Chinese Loess Plateau, Central Asian loess-paleosol sequences remain poorly understood. Here, we present an aeolian loess section in the southern Ili Basin. Based on granularity and mineralogical analyses, we reconstruct climatic changes during the last glaciation. The results indicated that most of the abrupt climatic events (such as Dansgaard-Oeschger events and Heinrich events) were imprinted in this loess section, although their amplitudes and ages showed some differences. Compared with the millennial oscillations recoded in loess and stalagmites in East Asia, the arid Central Asia responded more sensitively to the warming events than to the cooling events. The shifting trajectory of westerlies across Central Asia played an important role in dust deposition during the stadials. The North Atlantic climatic signals may have been transmitted from Central Asia to the East Asian monsoon regions via the westerlies

Demonstration of the first monolithically integrated self-rolled-up tube based vertical photonic coupler

We demonstrated the first monolithically integrated self-rolled-up SiN_x tube based vertical photonic coupler on top of a planar ridge waveguide. The coupling efficiency between the elements is >10 times higher than similar non-integrated device

Strain prioritization and genome mining for enediyne natural products

The enediyne family of natural products has had a profound impact on modern chemistry, biology, and medicine, and yet only 11 enediynes have been structurally characterized to date. Here we report a genome survey of 3,400 actinomycetes, identifying 81 strains that harbor genes encoding the enediyne polyketide synthase cassettes that could be grouped into 28 distinct clades based on phylogenetic analysis. Genome sequencing of 31 representative strains confirmed that each clade harbors a distinct enediyne biosynthetic gene cluster. A genome neighborhood network allows prediction of new structural features and biosynthetic insights that could be exploited for enediyne discovery. We confirmed one clade as new C-1027 producers, with a significantly higher C-1027 titer than the original producer, and discovered a new family of enediyne natural products, the tiancimycins (TNMs), that exhibit potent cytotoxicity against a broad spectrum of cancer cell lines. Our results demonstrate the feasibility of rapid discovery of new enediynes from a large strain collection. IMPORTANCE Recent advances in microbial genomics clearly revealed that the biosynthetic potential of soil actinomycetes to produce enediynes is underappreciated. A great challenge is to develop innovative methods to discover new enediynes and produce them in sufficient quantities for chemical, biological, and clinical investigations. This work demonstrated the feasibility of rapid discovery of new enediynes from a large strain collection. The new C-1027 producers, with a significantly higher C-1027 titer than the original producer, will impact the practical supply of this important drug lead. The TNMs, with their extremely potent cytotoxicity against various cancer cells and their rapid and complete cancer cell killing characteristics, in comparison with the payloads used in FDA-approved antibody-drug conjugates (ADCs), are poised to be exploited as payload candidates for the next generation of anticancer ADCs. Follow-up studies on the other identified hits promise the discovery of new enediynes, radically expanding the chemical space for the enediyne family

MOLECULAR MECHANISMS OF THROMBOXANE A2 RECEPTOR-MEDIATED INVASION IN LUNG CANCER CELLS

Thromboxane A2 receptor (TP) has been shown to play important roles in multiple aspects of cancer development including regulation of tumor growth, survival and metastasis. Molecular mechanisms of TP mediated cancer cell invasion remain to be identified. TP agonist, I-BOP, significantly elevated several matrix metalloproteinases (MMPs) including MMP-1, MMP-3, MMP-9 and MMP-10 in A549 human lung adenocarcinoma cells overexpressing TPα (A549-TPα) or TPβ (A549-TPβ). Signaling pathways of I-BOP-induced MMP-1 expression were examined in further detail as a model system for MMPs induction. Signaling molecules involved in I-BOP-induced MMP-1 expression were identified by using specific inhibitors including small interfering (si)-RNAs of signaling molecules and promoter reporter assay. The results indicate that I-BOP-induced MMP-1 expression is mediated by protein kinase C (PKC), extracellular signal-regulated kinase (ERK)-activator protein-1(AP-1) and ERK-CCAAT/enhancer-binding protein β (C/EBPβ) pathways. I-BOP-induced cellular invasiveness of A549-TPα cells was blocked by, GM6001, a general inhibitor of MMPs. Knockdown of MMP-1 and MMP-9 by their respective siRNA partially reduced I-BOP-stimulated A549-TPα cells invasion suggesting that other MMPs induced by I-BOP were also involved. Furthermore, secreted MMP-1 in conditioned media from I-BOP-treated A549-TPα cells (CM-I-BOP) autocrinely induced monocyte chemoattractant protein-1 (MCP-1) expression. The induction of MCP-1 by MMP-1 in A549 cells was via activation of protease-activated receptor 2 (PAR2) instead of commonly assumed PAR1. This conclusion was reached from the following findings: (1) expression of MCP-1 induced by trypsin, a PAR2 agonist, was inhibited by a PAR2 antagonist. (2) expression of MCP-1 induced by MMP-1 and by CM-I-BOP was blocked by a PAR2 antagonist but not by other PAR antagonists; (3) expression of MCP-1 induced by MMP-1 and by CM-I-BOP was attenuated significantly by pretreatment of cells with PAR2-siRNA. Finally, MCP-1 also can be induced by direct activation of TP in a SP1 involved mechanism. CM-I-BOP enhanced MCP-1-dependent migration of RAW 264.7 macrophages. Co-culture of A549 cells with RAW 264.7 macrophages induced expression of MMPs, VEGF and MCP-1 genes, and increased the invasive potential in A549 cells. My studies provide molecular mechanisms by which TP-mediated cancer cell invasion and suggest that TP is a potential anti-cancer drug target

Transgenic Eimeria magna Pérard, 1925 Displays Similar Parasitological Properties to the Wild-type Strain and Induces an Exogenous Protein-Specific Immune Response in Rabbits (Oryctolagus cuniculus L.)

Rabbit coccidiosis causes great economic losses to world rabbitries. Little work has been done considering genetic manipulation on the etiological agents, rabbit Eimeria spp. In this study, we constructed a transgenic line of Eimeria magna (EmagER) expressing enhanced yellow fluorescent protein (EYFP) and red fluorescent protein (RFP) using regulatory sequences of Eimeria tenella and Toxoplasma gondii. We observed the life cycle of EmagER and confirmed that the transgenic parasites express exogenous proteins targeted to different cellular compartments throughout the entire life cycle. EYFP was expressed mainly in the nucleus and RFP both in the nucleus and cytoplasm. Then, coccidia-free, laboratory-reared 40-day-old rabbits were primarily infected with either EmagER or wild-type strain oocysts and challenged with the wild-type strain. EmagER showed similar reproductivity and immunogenicity to the wild-type strain. Finally, we examined the foreign protein-specific immune response elicited by EmagER. Rabbits were immunized with either transgenic or wild-type oocysts. Immune response against parasite-soluble antigen, EYFP and RFP in spleen, and mesenteric lymph nodes were detected by quantitative real-time PCR. The relative expression level of IFN-γ, IL-2, and TNF-α were higher in EmagER-immunized rabbits than wild-type parasites-immunized rabbits after stimulation with EYFP and RFP. Our study confirmed that a specific immune response was induced by the exogenous protein expressed by EmagER and favored future studies on application of transgenic rabbit coccidia as recombinant vaccine vectors

Study on Growth and Change of Solid Particles with Water Flow in Oilfield Water-Injection Pipeline

The solid particles in oilfield water-injection pipelines with water flow will continuously grow and change, and the oversized solid particles may block the pores of the formation and reduce the oilfield recovery efficiency. Therefore, the study on the growth and change to solid particles during transportation has become a question of interest in oilfields. However, there is little research on this question currently. Therefore, on the basis of the liquid-solid two-phase flow model and the particle population balance model, a growth and change model of solid particles in long-distance water-injection pipelines flowing along water was established in this paper in consideration of the injected water temperature drop along the path, as well as the growth, coalescence, breakage and deposition of particles. Comparison of the field test results indicated that the average error of the particle size distribution fitting degree calculated by the model is 6.9%, and the average error of median diameter is 4.1%. This model was used for analyzing the impact of the flow rate, temperature and median diameter of the united station outlet in a block oilfield of Shengli Oilfield on the solid particle size of the wellheads, and the critical flow rate, temperature and median diameter of the united station outlet were predicted when the median diameter at the wellheads meets the injection requirement (< 2 μm). The establishment of this model cannot only be used for the study on the growth and change to solid particles in water-injection pipelines flowing along water, but also provides a technical reference for the study on the growth and change to low-concentration solid particles accompanying flow in long-distance liquid/gas phase pipelines

Optimizing Technology of Drilling Fluid for Improving Logging Success Rate of Central Area of Junggar Basin

The characters of deep wells in the central area of Junggar Basin include the burial depth of the reservoir is deep, the temperature of borehole bottom is high and the middle and the lower formations are developed with hard and brittle mudstones. The Toutunhe Formation and the Badaowan Formation are full of micro fissures which frequently caused sloughing, borehole wall collapse to happen. The average well diameter expansion rate exceeds 15% and logging instruments got blocked frequently. Based on the analyses of mineral composition and physical and chemical properties, Optimized drilling fluid formula was presented after evaluation of different size plugging agents and lubricants in order to heighten tight plugging performance. The result of Pressure Transmission experiment indicates that after optimization drilling fluid can prevent or stay the pressure transmission in mudstone effectively. The formula has been applied in Well Cheng 6 and the high-temperature and high-pressure filtration loss was only 8.0mL, the average well diameter expansion rate was less than 5%. The logging success rate reached 100%, exceeding the research target of 80%. Using this formula, the goals of stabilizing borehole wall and enhancing logging success rate have been achieved