通过超宽139La固体核磁共振波谱研究层状La(OH)2NO3

层状稀土氢氧化物是一类新型的稀土功能材料，本文采用固体核磁共振（SSNMR）方法研究了同时具备离子交换能力和非线性光学特性的层状La（OH）₂NO₃化合物，探讨了通过四极核CPMG（QCPMG）脉冲序列和变频谱图采集获取超宽¹³⁹La SSNMR谱图的方法，并描述了适用于此类实验的滤波方程和谱图重建方法.重建谱图同时包含四极核中心跃迁和卫星跃迁信息，本文使用QUEST软件对超宽¹³⁹La NMR谱图进行了模拟，获取的四极耦合常数C_Q和非对称因子η_Q均与CASTEP密度泛函理论计算值高度吻合.SSNMR实验结果证实层状La（OH）₂NO₃化合物属于非中心对称结构（P2₁），解决了对其结构长期以来存在的争论.     

Nucleus Independent Chemical Shift (NICS) at Small Distances from the Molecular Plane: The Effect of Electron Density

When close to the molecular plane, the behavior of nucleus independent chemical shift (NICS) as a function of the distance from the molecular plane deviates from its behavior at larger distances. By using a dense grid of NICS-probes (BQs) it is shown that, when close to the molecular plane, maximal (absolute) NICS values are obtained above the atoms. These maxima move towards the center as the grid is elevated until the (absolute) maximum NICS is obtained at the center and stay there when the grid is further elevated. It is shown that this behavior is a result of the current density, which is influenced by the electron density, according to the Biot-Savart law, which, in turn, causes the induced magnetic field measured by the NICS. It is thus concluded that if magnetic aromaticity is studied, the NICS calculations should be carried out at a large enough distance so that only the π-ring current affects the NICS. At distances ≥2 Å, NICS(r)_π,zz=A+B*C^r. Using non-linear correlation for obtaining A, B and C and extrapolate to NICS(1)_π,zz and NICS(1.7)_π,zz is recommended as measures for aromaticity.     

一种基于萘酰亚胺的检测细胞内pH值的荧光探针及其生物成像应用

细胞内溶酶体的pH值对细胞自噬、吞噬、酶加工等各项生命活动有着重要影响. 细胞核是真核细胞中最大的细胞器, 控制着生物体内的遗传和代谢过程, 参与代谢过程的酶对pH值的变化很敏感. 因此, 研究细胞体内的pH值变化至关重要. 我们设计并以简单的两步反应合成了一种新型荧光探针 NpH-1. 该探针以萘酰亚胺作为荧光团, 以吗啉基团作为对pH值响应的位点, 通过光诱导电子转移(PET)机制调控荧光, 能够对pH值变化响应. 我们在缓冲范围为1.81到11.92的Britton-Robison缓冲液中测定了 NpH-1对pH值变化响应的光谱性质. 在pH值3.0道10.0的范围内, NpH-1能够对pH值的变化产生快速可逆的响应, 其p Ka值为5.41. 探针具有很高的光稳定性. NpH-1具有很低的细胞毒性, 能够用于活细胞成像. 我们用氯喹刺激HeLa细胞, 使细胞的pH值发生变化, 并用探针 NpH-1监测了这一过程中的pH值变化. 另外, 还对 NpH-1进行了溶酶体、线粒体、高尔基体、内质网和细胞核的共定位实验, 结果表明, 探针主要分布在溶酶体和细胞核中, 这意味着 NpH-1可以用于检测复杂细胞环境中的pH值变化.     

Hypertension in Prenatally Undernourished Young-Adult Rats Is Maintained by Tonic Reciprocal Paraventricular–Coerulear Excitatory Interactions

Prenatally malnourished rats develop hypertension in adulthood, in part through increased α₁-adrenoceptor-mediated outflow from the paraventricular nucleus (PVN) to the sympathetic system. We studied whether both α₁-adrenoceptor-mediated noradrenergic excitatory pathways from the locus coeruleus (LC) to the PVN and their reciprocal excitatory CRFergic connections contribute to prenatal undernutrition-induced hypertension. For that purpose, we microinjected either α₁-adrenoceptor or CRH receptor agonists and/or antagonists in the PVN or the LC, respectively. We also determined the α₁-adrenoceptor density in whole hypothalamus and the expression levels of α_1A-adrenoceptor mRNA in the PVN. The results showed that: (i) agonists microinjection increased systolic blood pressure and heart rate in normotensive eutrophic rats, but not in prenatally malnourished subjects; (ii) antagonists microinjection reduced hypertension and tachycardia in undernourished rats, but not in eutrophic controls; (iii) in undernourished animals, antagonist administration to one nuclei allowed the agonists recover full efficacy in the complementary nucleus, inducing hypertension and tachycardia; (iv) early undernutrition did not modify the number of α₁-adrenoceptor binding sites in hypothalamus, but reduced the number of cells expressing α_1A-adrenoceptor mRNA in the PVN. These results support the hypothesis that systolic pressure and heart rate are increased by tonic reciprocal paraventricular–coerulear excitatory interactions in prenatally undernourished young-adult rats.     

Peripheral variation of heat transfer under pool boiling on tubes

Boiling heat transfer measurements on a tube designed to yield the peripheral variation of heat transfer coefficient without interfering with the nucleation site density are presented. A variation of up to 25% around the tube is found with a maximum at the base. High speed cine photography was used to estimate the variation of mean bubble layer thickness and mean velocities with angle. An iterative heat balance around the periphery indicated a voidage decrease from about unity at the base to 0.3–0.6 at 90°     

Improved general correlation for critical heat flux during upflow in uniformly heated vertical tubes

An improved version of the author's earlier correlation for CHF in vertical tubes is presented. It is compared with data that include 23 fluids (water, refrigerants, cryogens, chemicals, and liquid metals), tube diameters 0.315 to 37.5 mm, tube length 1.3 to 940 times diameter, mass flux 4 to 29051 kg/m²s, reduced pressures 0.0014 to 0.96, inlet quality −4 to +0.85, and critical quality −2.6 to +1. These data, from 62 independent sources, are also compared with Katto's general correlation and those of Bowring for water and Subbotin for helium. The present correlation shows much better agreement with data.     

Assessment of DFT functionals with fluorine–fluorine coupling constants†

Density functional theory (DFT) calculations of nuclear magnetic resonance (NMR) spin–spin coupling constants (SSCCs) provide an important contribution for understanding experimentally observed values. It is known that calculated SSCCs using DFT methods correlate well with those experimentally measured. Unlike most of SSCCs, in fluorine compounds, fluorine–fluorine SSCC J_FF shows that the Fermi contact (FC) term is not dominant, particularly for J_FF in polyfluorinated organic molecules. In order to devise a DFT approach that would correctly reproduce the variation of SSCCs within a series of fluorine compounds, we test several DFT-based approaches, using different exchange and correlation functionals. Isotropic contributions to NMR fluorine–fluorine coupling constants (FC, spin-dipolar, SD, paramagnetic spin-orbit, PSO, and diamagnetic spin-orbit, DSO) have been calculated. Results show that DFT methods give appropriate values for ⁿJ_FF (n = 4 to 7), while for geminal and vicinal J_FF present large deviations from experimental values. For the latter SSCCs (²J_FF and ³J_FF), the four contributions (FC, SD, PSO and DSO) are analysed as a function of the local and nonlocal exchange in 1,1- and 1,2-difluoroethylene. Although FC term is not dominant for these SSCCs, the variation of this contribution with exchange is remarkable. On the other hand, SD and PSO contributions can be suitably computed without and with exact exchange, respectively.     

On Vaporizing Water Flow in Hot Sub-Vertical Rock Fractures

Water injection into unsaturated fractured rock at above-boiling temperatures gives rise to complex fluid flow and heat transfer processes. Examples include water injection into depleted vapor-dominated geothermal reservoirs, and emplacement of heat-generating nuclear wastes in unsaturated fractured rock. We conceptualize fractures as two-dimensional heterogeneous porous media, and use geostatistical techniques to generate synthetic permeability distributions in the fracture plane. Water flow in hot high-angle fractures is simulated numerically, taking into account the combined action of gravity, capillary, and pressure forces, and conductive heat transfer from the wall rocks which gives rise to strong vaporization. In heterogeneous fractures boiling plumes are found to have dendritic shapes, and to be subject to strong lateral flow effects. Fractures with spatially-averaged homogeneous permeabilities tend to give poor approximations for vaporization behavior and liquid migration patterns. Depending on water flow rates, rock temperature, and fracture permeability, liquid water can migrate considerable distances through fractured rock that is at above-boiling temperatures and be only partially vaporized.     

Two-phase heat transfer correlation for multi-component mixtures in the saturated flow-boiling regime

Investigations of two-phase heat transfer in the saturated flow-boiling region for multi-component mixtures has led to a proposed new correlation for the heat transfer coefficient where heat transfer of boiling is simply expressed in terms of the boiling number. This correlation was tested against the existing data on forced convective boiling heat transfer reported in the literature, giving satisfactory results; the correlation should, however, be tested further against wider data on convective heat transfer coefficients in multicomponent systems. The present lack of such data should be remedied.     

A review of pool and forced convective boiling of binary mixtures

Boiling of binary mixtures is characterized by a close linking between heat and mass transfer processes, with the evaporation rate usually being limited by the mass transfer process. This is significantly different from single-component systems where interfacial mass transfer rates are normally very high. Information on pool boiling of binary mixtures is widely available in the literature, whereas research on forced convective boiling of mixtures has become significant only over the last few years. This paper presents a brief review of experimental results obtained in pool and forced convective boiling of binary mixtures and upgrades the empirical or theoretical predictive tools for both situations.