遮阴对黄波罗幼苗的光合特性及光能利用效率的影响

一直以来黄波罗(Phellodendron amurense)被认为是不耐阴树种,然而引入美国纽约后,发现它具有一定的耐阴性,在全光和林下均能更新,在纽约已经成为生物入侵种。为了探讨黄波罗的耐阴性问题,通过设置自然光与遮阴(15%自然光)两种光环境,观测了三年生黄波罗幼苗(遮阴1a后)光合生理参数、光能利用效率、叶绿素和比叶重的变化。结果表明,与自然光处理相比,遮阴处理的黄波罗幼苗最大光合速率、表观量子效率和暗呼吸速率略有下降,但差异不显著(p>0.05),光补偿点下降显著(p<0.05);同时,单位面积叶绿素含量无显著差异(p>0.05),而单位干重叶绿素含量显著升高,比叶重显著下降,叶面积显著增大(p<0.05)。上述结果说明:遮阴的黄波罗幼苗通过降低光补偿点和暗呼吸速率利用环境中的弱光,同时通过减小比叶重、增大叶面积和提高叶绿素b相对含量来增强对光的捕获,使其在弱光时的光能利用效率提高。由此推断,黄波罗幼苗能适应一定程度的遮阴。

温带阔叶红松林生态系统潜热通量模拟:气孔导度组合模型在Shuttleworth-Wallace双源模型中的应用(英文)

叶片水平的气孔导度组合模型已被成功扩展到冠层水平,并被应用于冬小麦生态系统潜热通量的模拟研究,但该研究仅基于1a的数据,有必要研究模型在更长时间尺度和其它生态系统类型的适用性。以长白山阔叶红松林(CBS)为研究对象,将组合模型进一步应用于Shuttleworth-Wallace双源模型,模拟了CBS3a生长季内的潜热通量,利用涡度相关系统观测的潜热通量数据对模型进行验证,并对比了双源模型与单源模型的模拟结果。结果显示,双源模型较单源模型能取得更高的模拟精度,生长季不同时期的潜热通量模拟值和实测值的日变化较

Rare-earth-metal mixed hydride/aryloxide complexes bearing mono(cyclopentadienyl) ligands. Synthesis, CO2 fixation, and catalysis on copolymerization of CO2 with cyclohexene oxide

Hydrogenolysis of mono(cyclopentadienyl)-ligated rare-earth-metal bis(alkyl) complexes Cp'Ln-(CH2SiMe3)2(THF) (Ln = Y (1a), Dy (1b), Lu (1c); Cp' = C5Me4SiMe3) with PhSiH3 afforded the mixed hydride/alkyl complexes [Cp'Ln(mu-H)(CH2SiMe3)(THF)](2) (Ln = Y (2a), Dy (2b), Lu (2c)). The overall structure of complexes 2a-c is a C-2-symmetric dimer containing a planar symmetric Ln(2)H(2) core at the center of the molecule. Deprotonation of ArOH (Ar = C6H2-Bu-t(2)-2,6-Me-4) by the metal alkyl group of 2a-c led to formation of the mixed hydride/aryloxide derivatives [Cp'Ln(mu-H)(OAr)](2) (Ln = Y (3a), Dy (3b), Lu (3c)), which adopt the dimeric structure through hydride bridges with trans-accommodated terminal aryloxide groups.

Alternating Copolymerization of Cyclohexene Oxide and Carbon Dioxide Catalyzed by Noncyclopentadienyl Rare-Earth Metal Bis(alkyl) Complexes

The syntheses of several dialkyl complexes based on rare-earth metal were described. Three beta-diimine compounds with varying N-aryl substituents (HL1 = (2-CH3O(C6H4))N=C(CH3)CH=C(CH3)NH(2-CH3O(C6H4)), HL2 = (2,4,6-(CH3)(3) (C6H2))N=C(CH3)CH=C(CH3)NH(2,4,6-(CH3)(3)(C6H2)), HL3 = PhN=C(CH3)CH(CH3) NHPh) were treated with Ln(CH2SiMe3)(3)(THF)(2) to give dialkyl complexes L(1)Ln (CH2SiMe3)(2) (Ln = Y (1a), Lu (1b), Sc (1c)), L(2)Ln(CH2SiMe3)(2)(THF) (Ln = Y (2a), Lu (2b)), and (LLu)-Lu-3(CH2SiMe3)(2)(THF) (3). All these complexes were applied to the copolymerization of cyclohexene oxide (CHO) and carbon dioxide as single-component catalysts.

Thiophene-NPN Ligand Supported Rare-Earth Metal Bis(alkyl) Complexes. Synthesis and Catalysis toward Highly trans-1,4 Selective Polymerization of Butadiene

A series of new rare-earth metal bis(alkyl) complexes [L(1-3)Ln(CH2SiMe3)(2)(THF)(n)] (L-1 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H2Me3-2,4,6: Ln = Sc, n = 1 (1a); Ln = Lu, n = 1 (1b); L-2 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H3Et2-2,6: Ln = Sc, n = 1 (2a); Ln = Lu, n = 1 (2b); Ln = Y, n = 1 (2c); L-3 = MeC4H2SCH2NC6H4(Ph)(2)P=(NC6H3Pr2)-Pr-i-2,6: Ln = Sc, n = 0 (3a)) and (LSc)-Sc-4(CH2SiMe3)(2()THF) (4a) (L-4 = C6H5CH2NC6H4(Ph)(2)P=NC6H3Et2-2,6) have been prepared by reaction of rare-earth metal tris(alkyl)s with the corresponding HL1-4 ligands via alkane elimination.

Isoprene polymerization with indolide-imine supported rare-earth metal alkyl and amidinate complexes

Reaction of 7-{(N-2,6-R)iminomethyl)}lindole (HL1, R = dimethylphenyl; HL2, R = diisopropylphenyl) and rare-earth metal tris(alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), generated new rare-earth metal bis(alkyl) complexes LLn(CH2SiMe3)(2)(THF) [L = L-1: Ln = Lu. (1a), Sc (1b); L = L-2 : Ln = Lu (3a), Se (3b)] and mono(alkyl) complexes L-2 Lu-2(CH2SiMe3) (4a). Treatment of alkyl complexes 1a and 4a with N,N'-diisopropylcarbodiimide afforded the corresponding amidinates (LLu)-Lu-1{iPr(2)NC(CH2SiMe3) NiPr2}(2) (2a) and L-2 Lu-2{iPr(2)NC(CH2SiMe3)NiPr2} (5a), respectively.

Highly 3,4-selective living polymerization of isoprene with rare earth metal fluorenyl N-heterocyclic carbene precursors

Fluorenyl modified N-heterocyclic carbene ligated rare earth metal bis(alkyl) complexes, (Flu-NHC)Ln(CH2SiMe3)2 (Flu-NHC = (C13H8CH2CH2(NCHCCHN)C6H2Me3-2,4,6); Ln = Sc (1a); Ln = Y (1b); Ln = Ho (1c); Ln = Lit (1d)), were synthesized and fully characterized by NMR and X-ray diffraction analyses. Complexes Ib-d with the activation of (AlBu3)-Bu-i and [Ph3C][B(C6F5)4] exhibited high activity, medium syndio-but remarkably high 3,4-regio-selectivity, and the unprecedented livingness for the polymerization of isoprene. Such distinguished catalytic performances could be maintained under various monomer-to-initiator ratios (500-5000) and broad polymerization temperatures (25-80 degrees C).

Synthesis, photophysical and electrophosphorescent properties of mononuclear Pt(II) complexes with arylamine functionalized cyclometalating ligands

Four cyclometalated Pt(II) complexes, i.e., [(L-2)PtCl] (1b), [(L-3)PtCl] (1c), [(L-2)PtC CC6H5] (2b) and [(L-3)PtC CC6H5] (2c) (HL2 = 4-[p-(N-butyl-N-phenyl)anilino]-6-phenyl-2,2'-bipyridine and HL3 = 4-[p(-N,N'-dibutyl-N'-phenyl)phenylene-diamino]-phenyl-6-phenyl-2,2'-bipyridine), have been synthesized and verified by H-1 NMR, C-13 NMR and X-ray crystallography. Unlike previously reported complexes [(L-1)PtCl] (1a) and [(L-1)PtC CC6H5] (2a) (HL1 = 4,6-diphenyl-2,2'-bipyridine), intense and continuous absorption bands in the region of 300-500 nm with strong metal-to-ligand charge transfer ((MLCT)-M-1) (d pi(Pt) -> pi*(L)) transitions (epsilon similar to 2 x 10(4) dm(3) mol (1) cm (1)) at 449-467 nm were observed in the UV-Vis absorption spectra of complexes 1b, 1c, 2b and 2c.

Rational Design, Synthesis, and Optical Properties of Film-Forming, Near-Infrared Absorbing, and Fluorescent Chiromophores with Multidonors and Large Heterocyclic Acceptors

A new series of film-forming, low-bandgap chromophores (1a,b and 2a,b) were rationally designed with aid of a computational study., and then synthesized and characterized. To realize absorption and emission above the 1000 nm wavelength, the molecular design focuses on lowering the LUMO level by fusing common heterocyclic units into a large conjugated core that acts an electron acceptor and increasing the charge transfer by attaching the multiple electron-donating groups at the appropriate positions of the acceptor core. The chromophores have bandgap levels of 1.27-0.71 eV, and accordingly absorb at 746-1003 nm and emit at 1035-1290 nm in solution. By design, the relatively high molecular weight (up to 2400 g mol(-1)) and non-coplanar structure allow these near-infrared (NIR) chromophores to be readily spin-coated as uniform thin films and doped with other organic semiconductors for potential device applications. Doping with [6,6]-phenyl-C-61 butyric acid methyl ester leads to a red shift in the absorption on]), for la and 2a. An interesting NIR electrochromism was found for 2a, with absorption being turned on at 1034 nm when electrochemically switched (at 1000 mV) from its neutral state to a radical cation state. Furthermore, a large Stokes shift (256-318 nm) is also unique for this multidonor-acceptor type of chromophore.

Rare-earth metal complexes stabilized by amino-phosphine ligand. Reaction with mesityl azide and catalysis of the cycloaddition of organic azides and aromatic alkynes

Stoichiometric reactions between mesityl azide (MesN(3), Mes = 2,4,6-C6H2Me3) and amino-phosphine ligated rare-earth metal alkyl, LLn(CH2SiMe3) (2)(THF) (L = (2,6-C6H3Me2)NCH2C6H4P(C6H5)(2); Ln = Lu (1a), Sc (1b)), amide, LLu(NH(2,6-(C6H3Pr2)-Pr-i))(2)(THF) (2) and acetylide at room temperature gave the amino-phosphazide ligated rare-earth metal bis(triazenyl) complexes, [L(MesN(3))]Ln[(MesN(3))-(CH2SiMe3)](2) (Ln = Lu (3a); Sc (3b)), bis(amido) complex [L(MesN3)] Lu[NH(2,6-C6H3 Pr-i(2))](2) (4), and bis(alkynyl) complex (5) (L(MesN(3))Lu (C CPh)(2))(2), respectively. The triazenyl group in 3 coordinates to the metal ion in a rare eta(2)-mode via N-beta and N-gamma atoms, generating a triangular metallocycle. The amino-phosphazide ligand, L(MesN(3)), in 3, 4 and 5 chelates to the metal ion in a eta(3)-mode via N-alpha and N-gamma atoms. In the presence of excess phenylacetylene, complex 3a isomerized to 3', where the triazenyl group coordinates to the metal ion in a eta(3) mode via Na and Ng atoms.

Reactivity of Rare-Earth Metal Complexes Stabilized by an Anilido-Phosphinimine Ligand

Treatment of anilido-phosphinimine-ligated yttrium mono(alkyl) complex 1a, LY(CH2Si(CH3)(3))(THF) (L = o-(2,6-(C6H3Pr2)-Pr-i)NC6H4P(C6H4)(C6H5)N(2,4,6-C6H2Me3)), with 2 equiv of phenylsilane in DME afforded methoxy-bridged complex 2, [LY(mu-OCH3)](2), via the corresponding hydrido intermediate. When excess isoprene was added to the mixture of la and phenylsilane, a eta(3)-isopentene product, 3, LY(CH2C(CH3)=CHCH3)(THF), was isolated. A lutetium chloride, LLuCl(DME) (4), was generated through the reaction of lutetium mono(alkyl) complex 1b, LLu(CH2Si(CH3)(3))(THF), with [Ph3C]-[B(C6F5)(4)]center dot LiCl accompanied by the formation of [Li(DME)(3)](+)[B(C6F5)(4)](-). Metathesis reaction of 1b with excess AlMe3 at room temperature gave a methyl-terminated counterpart, 5, LLu(CH3)(THF)(2). In all these reactions, the Ln-C-phenyl bonds of complexes 1 remained untouched.

Copolymerization of ethylene with norbornene catalyzed by cationic rare earth metal fluorenyl functionalized N-heterocyclic carbene complexes

Rare earth metal bis(alkyl) complexes attached by fluorenyl modified N-heterocyclic carbene (NHC) (Flu-NHC)Ln(CH2SiMe3)(2) (Flu-NHC = (C13H8CH2CH2(NCHCCHN)C6H2Me3-2,4,6); Ln = Sc (2a); Y (2b); Ho (2c); Lu (2d)), ((tBu)Flu-NHC)Ln(CH2SiMe3)(2) ((tBu)Flu-NHC = 2,7-(Bu2C13H6CH2CH2)-Bu-t(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (1a); Lu (1d)) and attached by indenyl modified N-heterocyclic carbene (Ind-NHC)Ln(CH2SiMe3)(2) (Ind-NHC = C9H6CH2CH2(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (3a); Lu (3d)), under the activation of (AlBu3)-Bu-i and [Ph3C][B(C6F5)(4)], showed varied catalytic activities toward homo- and copolymerization of ethylene and norbornene. Among which the scandium complexes, in spite of ligand type, exhibited medium to high catalytic activity for ethylene polymerization (10(5) g mol(Sc)(-1) h(-1) atm(-1)), but all were almost inert to norbornene polymerization. Remarkably, higher activity was found for the copolymerization of ethylene and norbornene when using Sc based catalytic systems, which reached up to 5 x 10(6) g mol(Sc)(-1) h(-1) atm(-1) with 2a. The composition of the isolated copolymer was varying from random to alternating according to the feed ratio of the two monomers (r(E) = 4.1, r(NB) = 0.013).

Alternating copolymerization of carbon dioxide and propylene oxide by single-component cobalt salen complexes with various axial group

A series of single-component cobalt salen complexes, N,N'-bis(salicylidene)-1,2phenylenediamino cobaltIII X(X = Cl (1a), Br (1b), NO3 (1c), CF3COO (1d), BF4 (le), and N3 (If)) (SalphCoX), were prepared for alternating copolymerization of carbon dioxide and propylene oxide(PO) under mild condition. The axial anion X group of the SalenphCoX played important role in tailoring the catalytic activity, polymeric/cyclic carbonate selectivity, as well as stereochemistry of carbonate unit sequence in the polymer chain. SalenphCoX with an electron-withdrawing axial X group (complex 1c) was an ideal catalyst for the copolymerization of CO2 and PO to selectively produce polycarbonate with similar to 99% carbonate linkage and over 81% head-to-tail structure.

新型吡啶双亚胺铁催化乙烯聚合反应

合成并表征了一种新型吡啶双亚胺铁烯烃聚合催化剂2,6-二[1-(4-羟基-2,6-二甲基苯胺)乙基]吡啶氯化铁(1a)。结果表明,在亚胺环的对位引入羟基,可同时提高催化剂的活性和聚合物的分子量。在改性甲基铝氧烷(MMAO)的活化下,该催化剂引发乙烯聚合的活性(以单位时间(h)molFe引发乙烯聚合的PE质量(g)来表征)可达到6.78×106g/(mol.h),明显高于催化剂2,6-二[1-(2,6-二甲基苯胺)乙基]吡啶氯化铁(1b),且能得到更高分子量的聚乙烯。

Synthesis, properties, and gas permeation performance of cardo poly(arylene ether sulfone)s containing phthalimide side groups

Novel bisphenol monomers (1a-d) containing phthalimide groups were synthesized by the reaction of phenolphthalein with ammonia, methylamine, aniline, and 4-tert-butylanilne, respectively. A series of cardo poly (arylene ether sulfone)s was synthesized via aromatic nucleophilic substitution of 1a-d with dichlorodiphenylsulfone, and characterized in terms of thermal, mechanical and gas transport properties to H-2, O-2, N-2, and CO2. The polymers showed high glass transition temperature in the range 230-296 degrees C, good solubility in polar solvents as well as excellent thermal stability with 5% weight loss above 410 degrees C. The most permeable membrane studied showed permeability coefficients of 1.78 barrers to O-2 and 13.80 barrers to CO2, with ideal selectivity. factors of 4.24 for O-2/N-2 pair and 28.75 for CO2/CH4 pair. Furthermore, the structure-property relationship among these cardo poly(arylene ether sulfone)s had been discussed on solubility, thermal stability, mechanical, and gas permeation properties. The results indicated that introducing 4-tert-butylphenyl group improved the gas permeability of polymers evidently.