Studying on countermeasures for deep processing of edible fungi in Gutian County

食用菌产业是古田县的支柱产业,发展精深加工对促进古田县食用菌产业转型升级具有重要意义。该文分析了古田县食用菌产业的发展现状及精深加工存在的主要问题,提出推动古田县食用菌产业向精深加工发展的对策。Mushroom industry is a pillar industry of Gutian County,to develop its deep processing had great significance to promote the transformation and upgrading of edible fungus industry.This paper analyzed present situation of edible mushroom industry development in Gutian County and the main problem in pushing on the development of deep processing,and put forward countermeasures for promoting the mushroom industry towards deep processing in Gutian County

cis-[Ni(NCS)_2tren]的镜面对称性破缺: 螯环的特殊手性构象

为了探究cis-[Ni(NCS)2tren][tren:三(2-氨基乙基)胺]的手性来源,本文采用单晶X射线衍射、溶液紫外-可见-近红外(UV-Vis-NIR)光谱、固体紫外圆二色(CD)光谱和粉末X射线衍射(XRD)等对cis-[Ni(NCS)2tren]的一对手性晶体进行了表征.研究结果表明:该手性晶体由结晶过程中的镜面对称性破缺而形成;三角架型配体tren配位后的特殊手性构象(δδλ,λλδ)是cis-[Ni(NCS)2tren]的主要手性来源.络合物固体紫外CD谱所呈现的Cotton效应可能来自其螯环手性构象以及手性金属中心对NCS-配体的π-π*跃迁和荷移跃迁生色团的手性微扰.对20批次合成产物进行固体CD检测的统计结果表明:它们的对映体过量(ee)值在39%-100%之间

Inclusion Resolution of 1,1'-Bi-2-naphthol:Crystal Structure and CD Spectroscopy of the Inclusion Complexes

以d/l-缬氨醇为原料,通过二步反应得到价廉易得的拆分剂碘化(r)/(S)-n,n,n-三甲基-1-羟基-3-甲基-2-丁铵,采用包结拆分法,成功实现了对1,1′-联-2-萘酚(bInOl)的拆分.对具有(r)-构型的季铵盐与(r)-bInOl在甲醇中所形成包结物的晶体结构分析结果表明:I-离子桥联主体(拆分剂)的醇羟基和客体(bInOl)的酚羟基形成O-H…I-氢键,以及相邻层的主客体分子之间的C-H…O氢键相互作用是在包结物中实现手性识别的关键.同时对两个包结物的溶液和固体圆二色(Cd)光谱进行了研究.A highly efficient and environmentally friendly method for the resolution of racemic 1,1′-bi-2-naphthol (BINOL) was developed by inclusion complexation with the cheap and readily accessible (R)/(S)-N,N,N-trimethyl-1-hydroxyl-3-methyl-2-butanaminium iodide resolving agents, which were prepared by a simple two-step reaction starting with D/L-valinol.The X-ray structural analysis was carried out for the inclusion complex of the (R)-quaternary ammonium salt with (R)-BINOL in CH3OH.This showed that the O-H…I-hydrogen bonds among the bridged iodide anions with the alcoholic hydroxyl of the host (resolving agent) and the phenolic hydroxyls of the guests (BINOL) together with the C-H… O hydrogen-bond interactions between the host and guest molecules from the adjacent layers are responsible for the chiral recognition in the inclusion complex formation.In addition, the solution and solid-state circular dichiroism(CD) spectra of a pair of inclusion complexes were also carefully investigated.国家自然科学基金(20773098;20973136);广西化工研究院资助项目---

Mirror Symmetry Breaking of cis-[Ni(NCS)_2tren]: Special Chiral Conformations of Chelate Rings

为了探究CIS-[nI(nCS)2TrEn][TrEn:三(2-氨基乙基)胺]的手性来源,本文采用单晶X射线衍射、溶液紫外-可见-近红外(uV-VIS-nIr)光谱、固体紫外圆二色(Cd)光谱和粉末X射线衍射(Xrd)等对CIS-[nI(nCS)2TrEn]的一对手性晶体进行了表征.研究结果表明:该手性晶体由结晶过程中的镜面对称性破缺而形成;三角架型配体TrEn配位后的特殊手性构象(δδλ,λλδ)是CIS-[nI(nCS)2TrEn]的主要手性来源.络合物固体紫外Cd谱所呈现的COTTOn效应可能来自其螯环手性构象以及手性金属中心对nCS-配体的π-π*跃迁和荷移跃迁生色团的手性微扰.对20批次合成产物进行固体Cd检测的统计结果表明:它们的对映体过量(EE)值在39%-100%之间.In order to explore the chiral origin of cis-[Ni(NCS)2tren] [tren: tris(2-aminoethyl) amine], a pair of chiral crystals of cis-[Ni(NCS)2tren] was characterized by X-ray single crystal structural analysis, solution UV-Vis-near infrared (NIR) spectroscopy, solid state UV-circular dichiroism (CD), and powder X-ray diffraction (XRD) spectra.The results indicated that the chiral crystals of cis-[Ni(NCS)2tren] were obtained by mirror symmetry-breaking crystallization, and the special chiral ring conformations (δδλ, λλδ) of the coordinated tripod-type tren ligands are responsible for the chiral origin of cis-[Ni(NCS)2tren].The Cotton effects of Ni(II) complexes in the solid-state UV-CD spectra are presumably attributed to the π-π* and charge-transfer chromophores of the NCS- ligands by the chiral perturbation of the helical ring conformations and metal-centered chirality.According to the statistical results of solid-state CD spectra of cis-[Ni(NCS)2tren] for twenty batch syntheses, their enantiomeric excess (ee) values are between 39% and 100%.国家自然科学基金(20773098;20973136)资助项目---

Mirror Symmetry Breaking and Absolute Configuration Correlations of Fe(Ⅲ) Complexes with Achiral Substituted o-Iminobenzosemiquinonato Ligands

以2-苯胺基-4,6-二叔丁基苯酚(H2l) 和 fECl2·4H2O 为原料制备了一对手性半醌 fE(III) 络合物Λ-MEr-[fE(lISQ)3]和Δ-MEr-[fE(lISQ)3] (lISQ: 2-苯亚胺基-4,6-二叔丁基苯酚, MEr : 经式构型), 通过单晶 X 射线衍射分析结合单晶压制片膜的固体圆二色(Cd)光谱确定了该络合物的绝对构型, 在此基础上建立了此类半醌络合物[M(lISQ)3] (M=Cr, fE, CO)的惟手性金属中心绝对构型与固体 Cd 光谱之间的关联. 此外, 还对 10 份合成的[fE(lISQ)3]的大宗产物粉末与单晶的固体 Cd 谱进行了比对分析, 以及对 1 份合成产物进行 10 次重结晶的固体Cd 光谱表征. 研究表明该化合物在结晶过程中发生了镜面对称性破缺 (MSb), 对映体过量 (EE) 值在15%-100%之间.A pair of chiral o-iminobenzosemiquinonato Fe(Ⅲ) complexes, Λ-mer-[Fe(L ISQ ) 3 ] and Δ-mer- [Fe(L ISQ ) 3 ] (L ISQ : 2-phenylimino-4,6-di-tert-butylphenol, mer : meridian configuration), were synthesized from 2-anilino-4,6-di-tert-butylphenol (H 2 L) and FeCl 2 · 4H 2 O.Their absolute configurations were determined by single crystal X-ray diffraction (XRD) and solid-state circular dichroism (CD) spectra (the same single crystal for XRD was dispersed in KCl).Correlations between the absolute configurations of the chiral-at- metal o-iminobenzosemiquinonato M(Ⅲ) complexes [M(L ISQ ) 3 ] (M=Cr, Fe, Co) and their solid-state CD spectra were also established.Comparison between solid-state CD spectra of the bulk samples from 10 different syntheses and their single crystals were thoroughly analyzed.The solid-state CD spectra of the powdered samples from 10 different crystallizations of one product were characterized.These studies indicated that mirror symmetry breaking (MSB) occurred during the crystallization process of the Fe(Ⅲ) complexes and their enantiomeric excess (ee) values were between 15% and 100%.国家自然科学基金(21273175;20973136)资助项目~

Stereochemistry and solid-state circular dichroism spectroscopy of eight-coordinate chiral lanthanide complexes

本文立体选择性地合成了八配位ln(Ⅲ)络合物[Eu(dbM)3lrr](1)、[Eu(dbM)3lSS](2)和[Tb(dbM)3lrr](3)(lrr/lSS=(-)/(+)-4,5-蒎烯基联吡啶,HdbM=二苯甲酰甲烷),利用单晶衍射、uV-VIS和固体Cd光谱对其进行了表征.晶体结构分析和固体Cd光谱表明1和2互为对映体.采用激子手性方法,通过与六配位和七配位的β-二酮络合物的固体Cd光谱的对比,提出含β-二酮的八配位ln(III)络合物的绝对构型关联规则.该系列络合物的畸变四方反棱柱的Δ或Λ绝对构型也被其单晶结构所证实.Eight-coordinate chiral lanthanide complexes [Eu(dbm3LRR](1),[Eu(dbm)3LSS](2) and [Tb(dbm)3LRR](3) (LRR/L SS=(-)/(+)-4,5-pineno-2,2'-bipyridine,Hdbm=dibenzoylmethane) were synthesized stereoselectively,which were characterized by UV-vis,CD spectra and X-ray single-crystal diffraction.The mirror-image structure features of the complexes 1 and 2 were obtained by combination of the solid-state CD spectra and the crystal structure analysis.After further comparison with the solid-state CD spectra of six-coordinate and seven-coordinate metal complexes containing β-diketone ligands,the CD spectra-absolute configuration correlation rule for the eight-coordinate β-diketonate lanthanide complexes was proposed through the exciton chirality method for the first time.The Δ or Λ absolute configurations of the complexes 1～3 with the distorted square antiprism geometry were confirmed by X-ray single-crystal analysis.国家自然科学基金(批准号:20773098;20973136);厦门大学科技创新工程基金(系列2)(批准号:XDKJCX20061027)资

Synthesis,characterization,structures and magnetic properties of chiral oxalate-bridged dicopper(Ⅱ) complexes

通讯作者, E-mail: [email protected]; [email protected][中文文摘]分别以(8R,10R)-(−)-[4,5]-pineno-2,2′-bipyridine 或(8S,10S)-(+)-[4,5]-pineno-2,2′-bipyridine (LRR 和LSS)为手性配体合成双核铜络合物[Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2] (1)、[Cu2(μ-ox)(LRR)2 (CH3COCH3)2(ClO4)2] (1a)、[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2] (2)和[Cu2(μ-ox)-(LRR)(LSS)(CH3COCH3)2 (ClO4)2] (3) (ox2− = 草酸根), 并探讨了其反应机理. 由元素分析、电导率、紫外可见谱(UVvis) 、圆二色(CD)谱和晶体结构分析推测: 该系列络合物具有草酸根桥联的双核结构, 两个铜 (II)离子与草酸根几乎成共平面; 1a 和3 的晶体结构分析表明, 每个Cu(II)的配位构型为拉长畸 变八面体, 双核分子中轴向的两个溶剂分子和两个高氯酸根互为反式配位. 对映体络合物1 和2 的溶液CD 光谱大致呈镜像对称, 在可见区的极弱CD 吸收峰可能源于LRR 和LSS 蒎烯基 上的手性中心对Cu(II)d-d 生色团的手性微扰产生的邻位效应. 采用最小二乘法和 Bleaney-Bowers 方程对络合物1 的变温磁化率测试数据进行拟合, 求得交换积分J = −338.41(4) cm−1, 表明铜(II)离子间有较强的反铁磁自旋交换作用.[英文文摘]The oxalato-bridged dicopper(II) complexes [Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2] (1), [Cu2(μ-ox) (LRR)2(CH3COCH3)2(ClO4)2](1a), [Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2] (2) and [Cu2(μ-ox)(LRR)(LSS)2 (CH3COCH3)2- (ClO4)2] (3) [LRR = (8R,10R)-(−)-[4,5]-pineno-2,2'-bipyridine, LSS = (8S,10S)-(+)- [4,5]-pineno-2,2'-bipyridine; ox2− = oxalate] were first prepared. A possible mechanism for the formation of the chial dicopper(II) complexes was proposed. Based on elemental analysis, conductance measurement, UV-vis spectra, CD spectra and X-ray single-crystal diffraction, the oxalato-bridged structures of 1 and 2 were deduced to adopt two Cu(II) ions and the bridged oxalate lying in the nearly same plane. The crystal structures of 1a and 3 reveal that the coordination geometry around each Cu(II) ion is an elongated and distorted octahedron and two axial solvent molecules and two perchlorate ions are anti to each other respectively in both binuclear molecules. The solution CD spectra of 1 and 2 in the visible d-d range show very weak Cotton effects with peaks at 588 and 779 nm, which are approximately of mirror image, suggesting the optical activities may be derived from the vicinal effects of the chiragenic centers at the pinene group of LRR and LSS, respectively. The complex 1 has been characterized by variable-temperature magnetic susceptibility and the data was least-square fitted to the Blenaey-Bowers equation. The exchange integral J was found to be –338.41(4) cm−1, indicating a strong antiferromagnetic interaction between two copper(II) ions.国家自然科学基金(20773098&20973136); 厦门大学科技创新工程基金(系列2)(XDKJCX20061027)资