Carbophile Additionen von Organocupraten mit 1,3-Thiazol-5(4H)-thionen

Carbophilic Additions of Organocuprates and 1,3-Thiazole-5(4H)-thiones Organocuprates and 1,3-thiazole-5(4H)-thiones 1 react in THF at 0° via carbophilic addition onto the C? S bond to give 4,5-dihydro-1,3-thiazole-5-thiols 3 (Scheme 3). This observation is in marked contrast to the previously described reaction of organolithium compounds and 1 , which undergo a thiophilic addition onto the exocyclic S-atom. As an exception, treatment of the 1,3-thiazole-5(4H)-thione 1a with tert-butyl cuprate leads to 7a (Scheme 3).     

Synthesis of monodisperse polymers from proteins

Proteins are functional biopolymers; viewed as molecules, they are also monodisperse polyamides with chemically reactive side chains. This paper describes the use of proteins as starting materials for the synthesis of monodisperse polymers with nonbiological functionalities attached to the side chains. It demonstrates the complete derivatization of amine groups (lysine side chains and N-termini) on three different proteins by addition of activated carboxylate reagents in aqueous solutions containing sodium dedecyl sulfate (SDS), under denaturing conditions. Several different acylating reagents were used to generate derivatized proteins; the resulting compounds constitute a new class of monodisperse, semisynthetic polymers, having the potential for wide variation in the structure of the backbone and of the side chains. Modification of lysozyme on a gram scale demonstrated that the method can generate useful quantities of material.     

Prominin‐1‐Specific Binding Peptide‐Modified Apoferritin Nanoparticle Carrying Irinotecan as a Novel Radiosensitizer for Colorectal Cancer Stem‐Like Cells

Resistance of cancer stem cells to radiotherapy remains a major obstacle to successful cancer management. Prominin‐1 (PROM1) is a cancer stem cell marker. Nanoparticle (NP) chemotherapeutics preferentially accumulate in tumors and are able to target cancer and cancer stem‐like cells through cancer cell‐specific ligands, making them uniquely suited as radiosensitizers for chemoradiation therapy. Using a biocompatible apoferritin NP, a PROM1‐targeted NP carrying irinotecan (PROM1‐NP) is engineered. The synergistic effect of the NP and irradiation is evaluated in PROM1‐overexpressing HCT‐116 colorectal cancer cell lines in vitro and in vivo. PROM1‐NP has a size of 17.2 ± 0.2 nm and surface charge of ?13.5 ± 0.2 mV. It demonstrates higher intracellular uptake than nontargeted NP or irinotecan alone. Treatment with PROM1‐NPs decreases HCT‐116 cell proliferation in a dose‐ and time‐dependent manner. In vitro radiosensitization reveals that PROM1‐NP is significantly more effective as a radiosensitizer than nontargeted NP or irinotecan. HCT‐116 tumor xenograft growth is markedly slower following treatment with PROM1‐NP plus irradiation, suggesting that PROM1‐NP is more effective as a radiosensitizer than irinotecan and nontargeted NP in vivo. This study provides the first preclinical evidence of the effectiveness of PROM1‐targeted NP formulation of irinotecan as a radiosensitizer.     

Use of hyperpolarized [1-C]pyruvate and [2-C]pyruvate to probe the effects of the anticancer agent dichloroacetate on mitochondrial metabolism in vivo in the normal rat

Development of hyperpolarized technology utilizing dynamic nuclear polarization has enabled the measurement of ¹³C metabolism in vivo at very high signal-to-noise ratio (SNR). In vivo mitochondrial metabolism can, in principle, be monitored with pyruvate, which is catalyzed to acetyl-CoA via pyruvate dehydrogenase (PDH). The purpose of this work was to determine whether the compound sodium dichloroacetate (DCA) could aid the study of mitochondrial metabolism with hyperpolarized pyruvate. DCA stimulates PDH by inhibiting its inhibitor, pyruvate dehydrogenase kinase. In this work, hyperpolarized [1-¹³C]pyruvate and [2-¹³C]pyruvate were used to probe mitochondrial metabolism in normal rats. Increased conversion to bicarbonate (+ 181±69%, P=.025) was measured when [1-¹³C]pyruvate was injected after DCA administration, and increased glutamate (+ 74±23%, P=.004), acetoacetate (+ 504±281%, P=.009) and acetylcarnitine (+ 377±157%, P=.003) were detected when [2-¹³C]pyruvate was used.     

Unconditionally convergent nonlinear solver for hyperbolic conservation laws with S-shaped flux functions

This paper addresses the convergence properties of implicit numerical solution algorithms for nonlinear hyperbolic transport problems. It is shown that the Newton–Raphson (NR) method converges for any time step size, if the flux function is convex, concave, or linear, which is, in general, the case for CFD problems. In some problems, e.g., multiphase flow in porous media, the nonlinear flux function is S-shaped (not uniformly convex or concave); as a result, a standard NR iteration can diverge for large time steps, even if an implicit discretization scheme is used to solve the nonlinear system of equations. In practice, when such convergence difficulties are encountered, the current time step is cut, previous iterations are discarded, a smaller time step size is tried, and the NR process is repeated. The criteria for time step cutting and selection are usually based on heuristics that limit the allowable change in the solution over a time step and/or NR iteration. Here, we propose a simple modification to the NR iteration scheme for conservation laws with S-shaped flux functions that converges for any time step size. The new scheme allows one to choose the time step size based on accuracy consideration only without worrying about the convergence behavior of the nonlinear solver. The proposed method can be implemented in an existing simulator, e.g., for CO₂ sequestration or reservoir flow modeling, quite easily. The numerical analysis is confirmed with simulation studies using various test cases of nonlinear multiphase transport in porous media. The analysis and numerical experiments demonstrate that the modified scheme allows for the use of arbitrarily large time steps for this class of problems.     

香港大学在束伽玛谱学研究与新一代伽玛探测器阵列(英文)

探索原子核的壳层演化,验证奇特核的幻数结构是香港大学核物理研究的重要方向。目前,科研团队利用在束伽玛谱学技术已经研究了30Ne的N=20幻数消失和78Ni（Z=28,N=50）附近原子核的双幻数结构,而即将开展的53,56Ca在束伽玛谱学实验会对新幻数N=34的定量研究,以及到N=40核的壳层演化提供重要的数据。下一步的研究目标是探索100Sn（N=Z=50）的奇特结构,特别是研究它的第一个2+激发态与其邻近原子核的低激发态性质。100Sn处于质子滴线以及核天体快质子俘获路径上,因此,它的幻数结构及其临近原子核单粒子性能研究将会极大增强对核力和核合成机制的认识。为了进一步提高物理实验统计,香港大学在数量上增加了30% NaI（Tl）晶体从而全面升级了DALI2伽玛探测阵列。此外,为了探索远离稳定线核区的新物理,开展更高精度在束伽玛谱学实验,香港大学与中国科学院近代物理研究所、中国原子能科学研究院计划合作研制基于溴化镧晶体的新一代伽玛探测器阵列。这套阵列主要在兰州重离子加速器（HIRFL）和将来建成的强流重离子加速器（HIAF）等大科学装置上开展实验,从而在奇特核研究方面取得大量重要的成果,促进科研人员全面认识、理解核力以及天体核合成过程。Exploring the evolution of shell closures and examining the magicity of extremely exotic nuclei are the main research interests of HKU (University of Hong Kong) experimental nuclear physics group. The group has employed in-beam gamma-ray spectroscopy technique to investigate the vanishing of N=20 magicity in 30Ne (N=20) and the strong magicity in nuclei around 78Ni (Z=28, N=50). The approved future's experiment on spectroscopy of 53,56Ca, proposed by HKU, will give quantitative information for the "magic index" of N=34 and shell evolution toward N=40. The next goal is to investigate the structure of 100Sn (N=Z=50), particularly the energy of the first 2+ state, and the low-lying states in the neighboring nuclei. 100Sn lies on the proton drip-line and on the astrophysical rp-process path. Characterizing the magicity of 100Sn and the nature of single-particle states in its neighboring nuclei is therefore essential to the fundamental understanding of nuclear forces and nucleo-synthesis. To significantly increase the data statistics for our physics goals, HKU group has prepared the upgrade of gamma-ray spectrometer DALI2 with 30% more NaI(Tl) detectors integrated into a new array configuration. On the other hand, next significant insights into the structure of nuclei would require new gamma-ray detection array capable for higher precision gamma-ray spectroscopy. HKU group in collaboration with IMP and CIAE therefore proposes to construct a new-generation gamma-ray detection array based on the novel scintillator LaBr₃(Ce) to explore the new physics in nuclei far from the valley of stability. Utilizing the radioactive beams at the Chinese large-scale facilities such as the Heavy Ion Research Facility in Lanzhou (HIRFL) in IMP and the future's High Intensity heavy-ion Accelerator Facility (HIAF), this novel LaBr₃(Ce) array would lead to a significant boost to the frontiers of exotic-nuclei research, which will guide scientists towards the comprehensive and even beyond-traditional understanding of nuclear forces and nucleosynthesis.     

Detection of nanoparticles in edible plant tissues exposed to nano-copper using single-particle ICP-MS

The increasing use of nanopesticides has raised concerns about their effects on crop plants and the impact of human health as well as ecological effects. While increased uptake of metal ions has been observed before, to date, very few studies have demonstrated the presence of nanoparticles in edible tissues. Single-particle inductively coupled plasma–mass spectrometry (sp-ICP-MS) has been suggested as a powerful tool to detect inorganic nanoparticles (NPs) in environmental samples. Here, we exposed edible plant tissues from lettuce, kale, and collard green to nano-CuO, simulating its use as a nanopesticide. We applied sp-ICP-MS to demonstrate the presence of nanoparticles, both in the water used to rinse crop leaf surfaces exposed to nano-CuO and within the leaf tissues. Lettuces retained the highest amounts of nCuO NPs on the leaf surface, followed by collard green and then kale. Surface hydrophilicity and roughness of the leaf surfaces played an important role in retaining nano-CuO. The results indicate that most of the nanoparticles are removed via washing, but that a certain fraction is taken up by the leaves and can result in human exposure, albeit at low levels.

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Synthesis and characterization of graphene-based nanocomposites with potential use for biomedical applications

In this paper, GaN nanoparticles were synthesized from the complex Ga(H₂NCONH₂)₆Cl₃ in the flow of NH₃ at a mild temperature (350 °C). Further purification was performed by the ethanol-thermal method. The ethanol-thermal method also prompted the GaN nanoparticles to grow into an anisotropic morphology. XRD patterns reveal that GaN nanoparticles have crystallized in a hexagonal wurtzite structure. TEM observation shows that the average size of the as-prepared nanoparticles is about 5–10 nm. The photoluminescence spectrum exhibits a broad green emission band with a peak at 510 nm. It can be known from the first-principle theoretic simulation by the TDDFT method that this fluorescence emission band is attributed to the hydride defects of V _N-H on the surface of GaN nanoparticles.     

Micromixing models for turbulent flows

In transported probability density function and filtered density function methods, micromixing models are required to close the molecular mixing term. The accuracy and computational efficiency of improved versions of the parameterized scalar profile (PSP) model are assessed and compared with commonly used mixing models such as Curl, modified Curl, interaction by exchange with the mean and Euclidean minimum spanning tree. Different generalizations of the PSP mixing model for spatially inhomogeneous flow configurations are presented. The selected test cases focus on molecular mixing and avoid interference with other models. Simulation results for a three-stream problem, involving two inert scalars, and a multi-scalar test case with mean-scalar-gradients are presented.     

PLD-assisted VLS growth of aligned ferrite nanorods, nanowires, and nanobelts-synthesis, and properties

We report here a systematic synthesis and characterization of aligned alpha-Fe2O3 (hematite), epsilon-Fe2O3, and Fe3O4 (magnetite) nanorods, nanobelts, and nanowires on alumina substrates using a pulsed laser deposition (PLD) method. The presence of spherical gold catalyst particles at the tips of the nanostructures indicates selective growth via the vapor-liquid-solid (VLS) mechanism. Through a series of experiments, we have produced a primitive "phase diagram" for growing these structures based on several designed pressure and temperature parameters. Transmission electron microscopy (TEM) analysis has shown that the rods, wires, and belts are single-crystalline and grow along <111>m or <110>h directions. X-ray diffraction (XRD) measurements confirm phase and structural analysis. Superconducting quantum interference device (SQUID) measurements show that the iron oxide structures exhibit interesting magnetic behavior, particularly at room temperature. This work is the first known report of magnetite 1D nanostructure growth via the vapor-liquid-solid (VLS) mechanism without using a template, as well as the first known synthesis of long epsilon-Fe2O3 nanobelts and nanowires.