Memory effects in gas chromatographic detection with a microwave-induced plasma

Capillary gas chromatography coupled to microwave-inducedplasma detection furnishes sensitivity adequate for trace analysis when the signal is monitored at a carbon emission line. Work performed with one of these systems at high electronic gain for the carbon signal has revealed solvent band widths in excess of four minutes; these impeded quantification of peaks eluting after the solvent. This report discusses two phenomena which could be related to the unexpected intensity of this solvent response: photomultiplier tube saturation and carbon deposits in the quartz plasma discharge tube.     

流动注射-ICP光谱分析中的基体效应和酸效应研究

本文讨论了流动注射-ICP光谱分析中的基体效应和酸效应。当基体(Na、Ca、Fe、Zn)的浓度大于5mg/ml时,待测元素的谱线强度表现出不同程度的降低;上述基体的引入对激发温度和电子密度的影响不明显;基体产生的抑制效应可能与改变了待测元素粒子的激发几率的因素有关;于载流体中加入一定量的基体元素,是消除或降低基体效应的有效方法。酸(HCl、HNO_3、H_2SO_4)对待测元素表现出不同程度的抑制效应,其主要原因是物理干扰所致。     

红外光谱中溶剂效应机理初探——配位机制的提出

本文就红外光谱中溶剂效应机理提出了溶质和溶剂分子间的瞬时配位作用机制，认为同－溶质在不同溶剂中的振动波数不同，是由于这种瞬时配位作用改变了溶质价电子运动状态所致。据此提出了溶剂效砂的定量关系式，测定了七种溶剂配位效应常数。用这一套经验参数处理了几种取代苯甲酸的羰基伸缩振动的溶剂效应，得较好的线性关系。还发现羰基的振动波数与取代基的Ｈａｍｍｅｔｔ常数σ之间，羰基伸缩振动对溶剂效应的敏感度与σ之间，Ｈ     

Quantum Thermal Effect of Dirac Particles in a Nonuniformly Rectilinearly Accelerating Black Hole with Electric Charge, Magnetic Charge, and Cosmological Constant

The Hawking radiation of Dirac particles in an arbitrarily rectilinearly accelerating Kinnersley black hole with electromagnetic charge and cosmological constant is investigated by using the generalized tortoise coordinate transformation. Both the location and the temperature of the event horizon depend on the time and the polar angle. The Hawking thermal radiation spectrum of Dirac particles is also derived.     

PARADOXICAL EFFECT OF A GnRH AGONIST ON STEROIDOGENESIS IN CULTURED MONKEY GRANULOSA CELLS

In this study we demonstrate: (i) The GnRH agonist exerts a direct dose-dependet stimulative effect on the aromatase activity and progesterone production in cultured monkey granulosa cells; (ii)the stimulative effect on steroidogenesis can be completely blocked by concomitant treatment with a GnRH antagonist, suggesting that the actions of GnRH are mediated through stringent stereospecific recongnition sites; (iii) in addition to the stimulative effect, the GnRH agonist in the presence of gonadotropins also exerts an inhibitory effect, even though the peptide by itself is more effective in the stimulation of steroidogenesis, and the stimulation of gonadotropin on steroidogenesis could be gradually restored by decreasing the concentration of the GnRH agonist in the culture; and (iv) paradoxical effect can also be observed in the presence of cAMP-inducing agents, suggesting that the inhibitory action of the peptide on gonadotropin-induced steroidogenesis is localized at a step distal to the stringent reco     

Transesterification of an RNA model in buffer solutions in H2O and D2O

Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H₂O and D₂O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pK_a), as the buffer concentration increases. The kinetic solvent deuterium isotope effect k_H/k_D, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd.     

AFM, SEM and GIXRD studies of thin films of red polycarbazolyldiacetylenes

In this paper we report the results of a morphological and structural investigation on film properties of a soluble polydiacetylene, the poly[1,6-bis(3,6-dihexadecyl-N-carbazolyl)-2,4-hexadiyne] (polyDCHD-HS). The red films of this polymer, prepared by standard spin-coating techniques, revealed absence of linear dichroism and birefringence in contrast with the ordered mesophases detected by powder X-ray studies. In order to interpret the optical behavior of this polymer, we performed AFM and SEM studies of polyDCHD-HS films spun on hydrophylic and hydrophobic glass substrates. We found the presence of surfaces organized in rod-like particles, more regularly oriented on the hydrophylic substrate. GIXRD studies, carried out on films sufficiently thick to allow the observation of the diffraction pattern, reveled the presence of a lamellar structure with a spacing of 3.22 nm. The low intensity of the diffraction peaks and the isotropic linear optical properties of the films show that the lamellar mesophases are not extended over large areas. These findings were compared with the data obtained from AFM and SEM studies on films of two other polydiacetylenes, the poly[1-(3,6-dihexadexyl-N-carbazolyl)-6-(N-carbazolyl)-2,4-hexadyine] (polya-DCHD) and the poly[1,6-bis(3,6-dipalmitoyl-N-carbazolyl)-2,4-hexadyine] (polyDPCHD), spun on hydrophylic glass substrate. The results confirmed the presence of nodular morphologies which seem to be a general characteristic of this class of materials. The particles organization appears instead related to the chemical nature of the substituents on the carbazolyl rings.     

Magnetic calorimeter for registration of small energy release

A scheme of magnetic calorimeter for registration of rare events characterized by small energy release (cosmic rays, WIMPs, solitary X-ray quanta) is proposed. The calorimeter is brought to operation by adiabatic demagnetization, and its magnetic response is measured by a quantum interferometer (SQUID, A. Barone and G. Paterno, Physics and applications of Josephson Effect). Special consideration is given to the specific features of calorimeter operation in the ferromagnetic transition region. The trigger registration of ultrasmall energy release by a ferromagnetic system in the metastable state is described.     

Analyzing the effect of the inventory policy on order and inventory variability with linear control theory

In this paper we apply linear control theory to study the effect of various inventory policies on order and inventory variability, which are key drivers of supply chain performance. In particular, we study a two-echelon supply chain with a stationary demand pattern under the influence of three inventory policies: an inventory-on-hand policy that bases orders on the visible inventory at an installation, an installation-stock policy that bases orders on the inventory position (on-hand plus on-order inventory) at an installation, and an echelon-stock policy that bases orders on the inventory position at that installation and all downstream installations. We prove analytically that the inventory-on-hand policy is unstable in practical settings, confirming analytically what has been observed in experimental settings and in practice. We also prove that the installation-stock and echelon-stock policies are stable and analyze their effect on order and inventory fluctuation. Specifically, we show the general superiority of the echelon-stock in our setting and demonstrate analytically the effect of forecasting parameters on order and inventory fluctuations, confirming the results in other research.     

The silicon effect on the regioselectivity of the Tsuji-Trost reaction. Experimental and theoretical approaches

Regioselectivity of the Tsuji-Trost reaction on allyl acetates and carbonates substituted with silyl groups at the olefinic moiety has been analyzed. Silicon atom in the central carbon atom increases the stability of the intermediate π-allylpalladium cation with respect to the isomeric π-allylpalladium cation featuring the silicon in a terminal carbon atom.