An unexpected Paternò-Büchi reaction in the crystalline state

[reaction: see text]. The solution and solid-state photochemistry of a series of aryl 1-phenylcyclopentyl ketones (1) was investigated. While typical Norrish type I products were formed in solution, irradiation of crystals of 1 afforded the novel oxetanes 3 and 4 regiospecifically. The formation of the oxetanes is believed to occur through Norrish type I cleavage and hydrogen abstraction, producing an alkene and an aldehyde, followed by a Paternò-Büchi reaction within the crystal lattice cage.     

The structure of new lignans from the seeds of phytolacca americana

From the seeds of Phytolacca americana two new lignans, Americanin B and D, have been isolated and their structures elucidated mainly by spectroscopic methods     

Field and flow programming in frit-inlet asymmetrical flow field-flow fractionation

The separation of wide molecular mass (Mr) ranges of macromolecules using frit inlet asymmetrical flow field-flow fractionation (FI-AFlFFF) has been improved by implementing a combination of field and flow programming. In this first implementation, field strength (governed by the cross flow-rate through the membrane-covered accumulation wall) is decreased with time to obtain faster elution and improved detection of the more strongly retained (high Mr) materials. The channel outlet flow-rate is optionally held constant, increased, or decreased with time. With circulation of the flow exiting the accumulation wall to the inlet frit, the dual programming of cross flow and channel outlet flow could be implemented using just two pumps. With this flow configuration, the channel outlet flow-rate is always equal to the channel inlet flow-rate, and these may be programmed independently of the cross flow-rate through the membrane. FI-AFlFFF retains its operational advantage over conventional asymmetrical flow FFF (AFlFFF). Unlike conventional AFlFFF, FI-AFlFFF does not require time consuming, and experimentally inconvenient, sample focusing and relaxation steps involving valve switching and interruption of sample migration. The advantages of employing dual programming with FI-AFlFFF are demonstrated for sets of polystyrene sulfonate standards in the molecular mass range of 4 to 1000 kDa. It is shown that programmed FI-AFlFFF successfully expands the dynamic separation range of molecular mass.     

Lanthanide triflate-catalyzed three component synthesis of alpha-amino phosphonates in ionic liquids. A catalyst reactivity and reusability study

The catalyst reactivity and reusability for the lanthanide triflate-catalyzed three component synthesis of alpha-amino phosphonates have been examined in room temperature ionic liquids, [bmim][X], in which the catalytic activities were very dependent on the counter anion, X, as well as on the phosphorus nucleophile, and moreover, the catalyst immobilized in an ionic liquid was reused several times without any loss of activity.     

Conformational analysis and electronic structure of acetanilide

The calculations of the electronic structure and conformational analysis of the acetanilide were carried out using the CNDO/2 method. The results show that the endo form is 1.2 Kcal/mole more stable than the exo form. The most stable conformation of the exo isomer corresponds to the dihedral angle of 90 ° between the phenyl and acetamide plane, whereas the minimum energy conformation of the endo isomer corresponds to the dihedral angle 50 °–60 °. A comparison of the calculated and experimental dipole moments suggests also the dihedral angle of 50 °–60 °. A comparison with experiment indicates that this molecular orbital method is good for conformational analysis and gives electronic structure which is compatible with spectroscopic measurement. The calculated conformational analysis and electronic structure of the acetanilide are in excellent agreement with experiments.We thank Professor J. P. Green for helpful discussions. This research was supported by a grant from the National Institute of Mental Health (MH-17489-01).     

Dye-sensitized solar cells based on composite solid polymer electrolytes

The ionic conductivity of polymer electrolytes and their interfacial contact with dye-attached TiO2 particles were enhanced markedly by the addition of amorphous oligomer into polymer electrolytes, resulting in very high overall energy conversion efficiency.     

一种新型的表面声波阻抗传感器及其在液相体系中的应用

一种新型的表面声波阻抗传感器及其在液相体系中的应用姚守拙，陈康，刘德忠，聂利华（湖南大学化学化工系，长沙，４１００８２）关键词表面声波，阻抗传感器，液相应用表面声波传感器（ＳＡＷＳ）具有较高的灵敏度和检测精度，已广泛应用于气体微量组分分析、色谱检测和...     

BBr3-promoted cyclization to produce ladder-type conjugated polymer

A novel chemical cyclization method using BBr₃ has been successfully developed to prepare ladder-type conjugated systems. The cyclized ladder compounds revealed an extended conjugation due to planarization of the structures. The extended ladder polymer can also be easily prepared by our chemical cyclization method using a soluble precursor.     

Rational design of an “all-in-one” phototheranostic

We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as “all-in-one” phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd³⁺ and Lu³⁺. The net result led to a metalloporphodilactol system, Gd-trans-2, with seemingly optimal ISC efficiency, photothermal conversion efficiency and fluorescence properties, as well as good chemical stability. Encapsulation of Gd-trans-2 within mesoporous silica nanoparticles (MSN) allowed its evaluation for tumour diagnosis and therapy. It was found to be effective as an “all-in-one” phototheranostic that allowed for NIR fluorescence/photoacoustic dual-modal imaging while providing an excellent combined PTT/PDT therapeutic efficacy in vitro and in vivo in 4T1-tumour-bearing mice.

We report here porphodilactol derivatives and their corresponding metal complexes as “all-in-one” phototheranostics by controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation.