Structures and Bonding Situation of Iron Complexes of Group‐13 Half‐Sandwich ECp* (E = B to Tl) Based on DFT Calculations

Quantum chemical calculations at the BP86 level with various basis sets (SVP, TZVPP, and TZ2P+) were carried out for the Fe(CO)₄ of group‐13 half‐sandwich ECp* [Fe(CO)₄‐ECp*] ( Fe4‐E ) (E = B to Tl). The chemical bonding of the Fe(CO)₄‐ECp* bond was analyzed with charge‐ and energy decomposition methods. The calculated equilibrium structures of complexes Fe4‐E show that the ligands ECp* are bonded in an end‐on way to the fragment Fe(CO)₄ in Fe4‐E with E = B to Ga. The compound Fe4‐In has a distorted end‐on ligand InCp*. In contrast, Fe4‐Tl has a side‐on bonded ligand TlCp*. The calculated bond dissociation energies (BDEs) suggest that the bond in the iron group‐13 half‐sandwich complexes Fe4‐E decreases from Fe4‐B to Fe4‐Tl . Natural bond orbital (NBO) analysis of the bonding situation reveals that the Fe(CO)₄←ECp* donation in Fe4‐E comes from the σ lone‐pair orbital of ECp*. Bonding analysis indicates that the ligand ECp* in complexes are strong σ donors and the NOCV pairs of the bonding show small π‐back donation from the Fe(CO)₄ to the ECp* ligands.     

RAFT链转移剂的选用原则及通用型RAFT链转移剂

可逆加成-断裂链转移聚合(RAFT Polymerization)是目前最为常用的活性可控自由基聚合方法之一,因其产物分子量分布较窄、适用单体范围广、反应条件温和等优势得到了不同领域科学家的广泛应用。然而,科学家们在选择RAFT链转移剂(也称RAFT试剂)时,经常会忽略RAFT链转移剂与单体活性的匹配原则,导致在制备高活单体与低活单体的嵌段共聚物方面存在产物分子量分布宽、聚合速率慢,甚至反应无法成功进行的问题。基于此,本文首先综述聚合中RAFT链转移剂的选用原则,随后介绍近几年开发的一类同时适用于高/低活性单体聚合的通用型RAFT链转移剂(Universal/Switchable RAFT agent)的作用原理及适用条件,并着重探讨了基于通用型RAFT链转移剂制备高/低活性单体的嵌段共聚物的最新进展及应用。     

Buckling analysis of functionally graded material (FGM) sandwich truncated conical shells reinforced by FGM stiffeners filled inside by elastic foundations

An analytical solution for buckling of an eccentrically stiffened sandwich truncated conical shell is investigated. The shell consists of two functionally graded material (FGM) coating layers and a core layer which are metal or ceramic subjected to an axial compressive load and an external uniform pressure. Shells are reinforced by stringers and rings, in which the material properties of shells and stiffeners are graded in the thickness direction following a general sigmoid law distribution. Two models of coated shell-stiffener arrangements are investigated. The change of the spacing between stringers in the meridional direction is taken into account. A couple set of three-variable-coefficient partial differential equations in terms of displacement components are solved by the Galerkin method. A closed-form expression for determining the buckling load is obtained. The numerical examples are presented and compared with previous works.     

Theoretical investigation of hot electron cooling process in GaAs/AlAs cylindrical quantum wire under the influence of an intense electromagnetic wave

Hot electrons cooling by phonons in GaAs/AlAs cylindrical quantum wire (CQW), under the influence of an intense electromagnetic wave (EMW), is studied theoretically. Analytic expression for the electron cooling power (CP) is derived from the quantum transport equation for phonons, using the Hamiltonian of interacting electron–optical phonon system. Both photon absorption and emission processes are considered. Numerical results show that the CP reaches maximum when the energy difference between electronic subbands equals the energy of an optical phonon plus the photon energy. Under the influence of the EMW, the negative CP is observed showing that electrons gain energy from phonon and photon instead of losing their energy. Also, the CP increases with increasing the EMW amplitude. Our results theoretically clarify the mechanism of the electron cooling process by phonons in the GaAs/AlAs CQW under the EMW, which is of significance for designing and fabricating high-speed nanoelectronic devices based on this material.     

Optical bistability in gaussian inhomogeneously broadened ring lasers with saturable absorber

The optical bistability (OB) in Gaussian inhomogeneously broadened ring lasers with saturable absorber (LSA) in both resonance and out-of-resonance is theoretically analyzed in the rate-equation approximation based on the dual two-level model. The OB effect may appear for appropriate sets of LSA control parameter values which can be displayed in phase diagrams. The characteristics of the OB curves as well as their stability behavior are analytically and numerically studied in detail. The influence of the control parameters, including detuning, are investigated and displayed in the figures. A brief comparison with the Lorentzian case is given as well. Paper submitted by authors in English April 20, 1999.     

Dragon Fruit Foliage: An Agricultural Cellulosic Source to Extract Cellulose Nanomaterials

In this report, we focus our effort to extract cellulose nanomaterials (CNs) from an agricultural cellulosic waste, Dragon Fruit foliage (DFF). DFF was first pretreated by several mechanical treatments and then bleached by chemical treatment to obtain bleached DFF. CNs were then produced from the hydrolysis of the bleached DFF catalyzed by sulfuric acid. We obtained CNs with a small diameter (50 to 130 nm) and length (100 to 500 nm) and a height of 3 to 10 nm. The CNs have a high crystallinity (crystallinity index 84.8%), high −COOH content (0.74 mmol·g⁻¹), good thermal stability and a good Cu (II) adsorption capacity with an adsorption maximum of ~103 mg·g⁻¹. These findings demonstrated the great potential of converting many agricultural cellulosic wastes into valuable cellulose nanomaterials.