Fluorescence Quenching Study of Zinc Bisporphyrins by Fulleropyrrolidines and Their N-Oxides

Novel phenylene-bridged zinc bisporphyrins （1-4）, fulleropyrrolidines （C60-m, C60-h） and their N-oxides （C60-mo, C60-ho） were synthesized. The fluorescence quenching processes of bisporphyrins in toluene solution by fulleropyrrolidines and their N-oxides were investigated by steady-state fluorescence spectra. The fluorescence quenching constants proved that the fluorescence quenching ability was decreased as reduction of the pyrrolidine functional groups of fullerene surface： C60-h〉C60-m〉C60, and the fluorescence quenching ability was increased about 1.3-7.4 times by utilizing fulleropyrrolidine N-oxides （C60-mo, C60-ho） compared to fulleropyrrolidine compounds （C60-m, C60-h）. The results revealed photoinduced electron transfer （PET） efficiency between bispor-phyrin and fullerene derivatives could be tunable by change of functional groups on fullerene surface.     

Transition-Metal-Free Catalyzed Dehydrative Coupling of Quinoline and Isoquinoline N-Oxides with Propargylic Alcohols

A novel,green,and transition-metal-free protocol for the facile modification of quinoline and isoquinoline derivatives is introduced,starting from readily available and environmentally benign quinoline and isoquinoline N-oxides with propargylic alcohols in the presence of Na₂S₂O₈ or K₂S₂O₈ at 100℃.The one-pot transformation features the advantages of good functional group compatibility,short reaction time,operational simplicity,and highly efficient reaction system.This protocol,which produces water as the only byproduct,provides efficient and atom-economical access to a class of fascinating quinoline and isoquinoline products in satisfactory yields.The method is effective on the gram scale,thus highlighting the inherent practicality of this methodology.     

Cinnamoylacetanilides and Their Metal Chelates

A new series of β-ketoanilides, in which the keto group attached to an olefinic linkage, have been synthesized by the reaction of acetoacetanilide with p-substituted benzaldehydes (4-methoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-dimethylaminobenzaldehyde and 4-nitrobenzaldehyde) under specified conditions. The existence of these β-ketoanilides predominantly in the intramolecularly hydrogen bonded enol forms has been well demonstrated from their IR, ¹H NMR and mass spectral data. Details on the formation of [ML₂] complexes of these compounds with Ni(II), Cu(II) and Zn(II) and their nature of bonding were discussed on the basis of analytical, IR, ¹H NMR and mass spectral data.     

Synthesis and Characterization of New Schiff Base and Polyoxa-azaCryptands and Their Rare Earth Cryptates with [1 1] Condensation and Reduction Methods

IntroductionWithspecialandnovelstructures,macropolycyclicmoleculespreselltamultitudeofnewproperties'andopenupvastvistasforapplicationsinmanyfields"',suchassupramoleculardevices,luminescentlabels,fluorescentprobesinbiologicalandmedicalapplications,magneticresonanceimagingandcatalyticcleavageofRNA,and.-theyarealsoimportantligands'forrecognizinginorganicandorganiccanons,anionsandneutralmolecules.Becauseofmulti-stepprocessandlowyields',thesynthesisofmacropolycycliccompoundsaresometimesverydifficu…     

Stromatolites Discovered in Nihewan Formation and Their Paleoenvironment

Columnar stromatolites have been discovered in two beds of the upper part of the Nihewan Formation, a series of lacustrine deposits. The structure of the stromatolites is characterized by alternation of light, intergranular pore-rich laminae and dark, organic substance-rich laminae. Abundant filamentous algal remains have been discovered in stromatolite laminae, some of them are similar to the species present on the shore of the Caribbean Sea that are living in warmer climate than in the Nihewan area now. With the ESR and U-series age methods, it has been determined that the ages of the lower and upper stromatolite beds are about 130,000 and 93,000 a B. P. , respectively. Compared with many other geologic events taking place during the period in Northern China, we conclude that the two stromatolite beds were formed during the two warmer stages of the Last Interglacial.     

Cosine Moments and Their Application to ∑ Relationships

Recent advances In the theory of ∑ relationships lead to the Investigation of moments needed to derive the relavant joint probability densities. These together with the linear theory of relationships, make possible the calcualtion of therelationships from ∑1 to ∑2 one by one. The superior performance ofour new ∑4 and ∑r relationships, for example, with respect to the older ∑1 and ∑3 formulas strongly suggests a deeper study of the pertinent moments. In this paper a new concept, the cosine moment, is introduced which, together with a certain integral theorem, permits the derivation of the relevant joint probability densities. These lead in turn to the derivation of all ∑ relationships valid for all the space groups.     

Preparation and Characterization of 2,2′-Dipicolyl Diselenide and Their Derivatives

Lithium 2-picolylselenolate/tellurolate is obtained by reacting lithiated 2-picoline with elemental selenium/tellurium which upon aerial oxidation gives 2,2'-dipicolyl diselenide in case of selenium while 1,2-bis(2-pyridyl)ethane in case of tellurium. Condensation of 2-picolylselenolate anion with a variety of electrophiles provides a facile synthesis of 2-picolylalkyl selenides in good to excellent yields. Quenching of lithiated 2-picoline with 2,2'-dipyridyl diselenide gives mixed 2-picolylseleno pyridine in low yield. All the compounds prepared are new and have been characterized by elemental analysis, 1 H NMR, 13 C NMR and mass spectral studies.     

Microtektites and Glassy Microspherules in Loess: Their Discoveries and Implications

It is first in continental sediment-loess that 16 microtektites and 3 ablated glassy Si-Mg microspherules were found. They occur only in the upper layer of L8, a 40—70-cm horizon above the B/M boundary. The age of deposition is about 0.72 Ma. Microtektites in loess are usually sphere, speroid, kidney-form, tear-drop and irregular debris in shape. They are transparent and translucent, and some have the shade of green, amber and yellow in color. Their sizes range from 65 to 220μm. Most of microtektites were badly pitted and corroded, but there remain bubbles, cavities and scorious and flow microstructure in some ones. On the basis of their major oxide compositions, microtektites in loess may be divided into three chemical groups that are described as normal, bottle-green and high-aluminium microtektite. They are similar in chemical composition to microtektites in deep-sea cores. Geochemistry of trace elements show that the origin of microtektite is very complicated and their parent materials are from mu     

Quaternary Derivatives of α- and β-Scopodonnines and Their Pharmacologic Activity

Several quaternary alkyl halides were synthesized from dimeric tropane alkaloids - and -scopodonnines, which were prepared by dimerization of hyoscine. Their pharmacologic activities were studied.     

Synthesis of Nonionic Oligomeric Manganese（ Ⅱ ） Complexes and Investigation of Their Toxicity and T1 -Relaxation Enhancement

Six nonionic oligomeric manganese （ Ⅱ ） complexes with oligomeric phosphate-polyglycol-EDTA ester ligands were synthesized and characterized. The longitudinal relaxivities of these complexes were measured. One of these complexes, which showed the highest relaxivity, was chosen to be used in the acute toxicity test and the T1-weighted imaging experiment. It has been found that compared to Gd-DTPA, this nonionic oligomeric Mn（ Ⅱ ） complex exhibits no acute toxicity, generates highly enhanced MRI signals and increases the intention time in the rat liver tissue.     

Synthesis of Nonionic Oligomeric Manganese(Ⅱ) Complexes and Investigation of Their Toxicity and Τ1-Relaxation Enhancement

Six nonionic oligomeric manganese(Ⅱ) complexes with oligomeric phosphate-polyglycol-EDTA ester ligands were synthesized and characterized. The longitudinal relaxivities of these complexes were measured. One of these complexes, which showed the highest relaxivity, was chosen to be used in the acute toxicity test and the Τ1-weighted imaging experiment. It has been found that compared to Gd-DTPA, this nonionic oligomeric Mn(Ⅱ) complex exhibits no acute toxicity, generates highly enhanced MRI signals and increases the intention time in the rat liver tissue.     

Studies on the Aromatic Dihalocarbonyl Ylides and Their Deoxygenation

The deoxygenation reaction of heptanones, cycloheptanone, cycloheptatrienone or substituted cycloheptatrienone with dihalo-carbene results in carbon monoxide and corresponding halides. The yield of CO produced by 2 , 4 , 6-triphenylcycloheptatrienone is 2.6-3.5 times as high as that produced by the saturated heptanones. The structures, energies, charge distributions, bond orders, and other relative parameters of the dihalocarbonyl glides were calculated by using the SCF-MNDO method. The obtained data reveal that the ylides from cycloheptatrienone have aromatic structure and are different from those produced from saturated cycloheptanone. The reactivities of the dihalocarbonyl ylides are discussed. It is proposed that this aromatic structure should be responsible for the high yield of CO from the reaction of cycloheptatrienone with dihalocarbene.     

Synthesis of Nonionic Oligomeric Manganese(Ⅱ) Complexes and Investigation of Their Toxicity andΤ_1-Relaxation Enhancement

Introduction Non-invasive and accurate imaging of human inter-nal organs is crucial for medical diagnosis. Lauterburand Mansfield were awarded the 2003 Nobel Prize inphysiology and medicine, respectively, for their semi-nal work concerning magnetic resonance imaging(MRI)[1]. This powerful technique represents a break-through in medical diagnostics as well as in other myri-ad fields such as chemistry, physics, materials scienceand biology. Throughout the development of the MRItechnique, a g…     

Synthesis and Structure of 1—Cyclopentylindenyl Lanthanide（Ⅱ）Complexes and Their Catalytic Behavior for Polymerization of Acrylonitrile

The reaction between K(1‐C₅H₉C₉H₆) and anhydrous LnCl₃ (Ln=Sm, Yb) in the molar ratio of 2:1 in THF with subsequent treatment by Na‐K alloy afforded (1‐C₅H₉C₉H₆)₂Ln‐(THF)_n(Ln=Sm, n=1; Ln=Yb, n=2), while the reaction of Sml₂ with K(1‐C₅H₉C₉H₆) in the molar ratio of 1:2 in THF gave the anionic complex K(1‐C₅H₉C₉H₆)₃Sm(THF)₃. The X‐ray structure of (1‐C₅H₉C₉H₆)₂Yb(THF)₂ showed that central metal Yb is coordinated by two cyclopentadienyl rings of 1‐cyclopentylindenyls and two oxygen atoms from two tetrahydrofuran molecules to form pseudo‐tetrahedral coordinate geometry. All these complexes are active for the polymerization of acrylonitrile.     

Synthesis and Characterization of Aryl Acylguanidines and Their Copper(Ⅱ) Complexes

A series of eight N-mono-substituted aryl acylguanidines L~(1～8) were synthesized from the reactions of their parent acylthioureas and respective primary amines, including five R~1C(O)N=C(NHR~2)_2 with balanced arms(denoted as R~1–R~2–R~2: Ph–Ar'–Ar', L~1(1); Ph–Ar'–Ar', L~2(2); 1-Naph–Ar'–Ar', L~3(3); 1-Naph–Ar'–Ar', L~4(4); 2-Naph–Ar'–Ar', L`5(5); Ar' = 2,6-Me_2C_6H_3, Ar' = 2,6-iPr_2C_6H_3) and three R~1C(O)N=C(NHR~2)NHR~3 with unbalanced arms(denoted as R~1–R~2–R~3: Ph–Ar'–Ph, L~6(6); Ph–Ar' –Ph, L~7(7); Ph–Ar' –Ar', L~8(8)). Treatment of L~(1～5)(1～5) with copper acetate in a molar ratio of 2:1 in dichloromethane led to the formation of homoleptic Cu(Ⅱ) complexes trans-L_2~(n')Cu(9～13), in which the Cu(Ⅱ) center was stabilized by deprotonated ligands Ln'(n = 1～5) in the O,N-bidentate mode. When similar reactions of L~6(Ph–Ar'–Ph)(6) and L~7(Ph–Ar'–Ph)(7) that contain unbalanced arms were investigated, the Cu(Ⅱ) products trans-L_2~(6')Cu(14) and trans-L_2~(7')Cu(15) were formed by deprotonating the bulky amine groups in Ln(-NHAr' for L~6 and-NHAr' for L~7) rather than the-NHPh group. In sharp contrast, trans-L_2~(8')Cu(16) was obtained from two-arm unbalanced L~8(Ph–Ar'–Ar')(8) not by deprotonating the more bulky-NHAr' group but the relatively less bulky-NHAr' group. In a further exploration, the reaction of 1:1 mixed ligands Ln and Lm with copper acetate was found to give only homoleptic Cu(Ⅱ) complex L_2~(n')Cu instead of the heteroleptic one L~(n')CuL~(m'). The in vitro antibacterial activity of L~n was evaluated against S. aureus, E. coli and C. albicans by determining the minimum inhibitory concentrations(MICs) using Kirby-Bauer test.     

Reaction of 2-Aminothiazoles and Their Benzo- and Naphtho Derivatives with β-Sulfonyltrifluoromethylvinyldiols

By cyclocondensation of 2-aminothiazoles and their benzo and naphtho analogs with -sulfonyltrifluoromethylvinyldiols, we have obtained a series of novel CF₃-containing 6,7-dihydro-5H-[1,3]thiazolo[3,2-a]pyrimidines. In the case of the sterically hindered 2-aminothiazoles, heterocyclization does not occur and the corresponding enamino ketones are formed.