Effect of permodified β‐cyclodextrin on the photophysical properties of poly[2,7‐(9,9‐dioctylfluorene)‐alt‐(5,5′‐bithiophene)] main chain polyrotaxanes

The photophysical properties of two polyrotaxanes ( PFBTh?PSβCD and PFBTh?PMeβCD ) composed of fluorene and bithiophene encapsulated into permodified β‐cyclodextrin cavities have been investigated and compared with those of the reference PFBTh . Rotaxane formation results in improvements of the thermal stability, solubility in common organic solvents, as well as better film forming ability combined with a high transparency. As expected PFBTh and its encapsulated forms absorb at wavelengths beyond 510 nm, and time‐resolved photoluminescence (PL) in solution shows a well‐define vibronic structures with a predominance of the 0‐0 transitions and an energy difference of 0.16 eV. The fluorescence lifetimes follow a monoexponential decay with a value τ = 630 ± 30 ps. Atomic force microscopy, AFM, indicated a tendency of polyrotaxanes to organize into fibers. The advancing contact angles indicated higher surface hydrophobicity and lower surface free‐energy values for polyrotaxanes compared with their unthreaded analogues. The device based on PFBTh?PSβCD: PCBM in a 1/1 w/w ratio under simulated AM 1.5G illumination at 100 mW cm^?2 exhibited improved photovoltaic parameters of cells, resulted in high V_oc (0.68 V), J_sc (1.65 mA cm^?2), FF (31.6%), and PCE (0.35) values, compared with PFBTh or PFBTh?PMeβCD , respectively. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 460–471     

Decisive Influence of Phosphorus Ligands on O2 Oxidations of Alkenes in the Presence of the Iron Nitrato/Iron Nitrosyl Couple

Abstract

Fe(NO)₂XL and Fe(NO)X₂L nitrosyl iron complexes, X = Cl, I, and L = HMPA, dppe, PPh₃, activate molecular O₂ to yield nitrato complexes. The phosphorous ligand is decisive for the oxidative power of these nitrates: with HMPA or dppe, oxygen transfer occurs only to phosphines. On going from HMPA to PPh3 the single nitrato complex obtained, Fe(NO)₂X(OPPh₃)₂ selectively epoxidizes cyclohexene, and this is the first example of oxygen transfer from a nitrato ligand to an olefin.     

SELECTIVE S-ALKYLATION IN PHASE TRANSFER CATALYSIS OF 2-PYRIDINE-, -PYRIMIDINE- AND BENZOXAZOLE-THIONE

Abstract

Alkylation via phase transfer catalysis of several ambident anions of the |N–C–S|^? type leads exclusively to S-substitution. Yields obtained are better or equal to those given by conventional methods and experimental work-up is very much simplified compared to the latter.     

Improved locally adaptive least-squares detection of differences in images

We introduce a method for change detection under nonuniform changes of intensity using an improved least-squares method. A locally adaptive normalizing window is correlated with the two images, and a morphological postprocessing is then applied to isolate objects that have been added or removed from the scene. We use a modification of the least-squares solution to get rid of clutter caused by intensity changes that do not satisfy the model assumed for the least-squares solution.     

Generalizations and Properties of the Principal Eigenvalue of Elliptic Operators in Unbounded Domains

Using three different notions of the generalized principal eigenvalue of linear second‐order elliptic operators in unbounded domains, we derive necessary and sufficient conditions for the validity of the maximum principle, as well as for the existence of positive eigenfunctions for the Dirichlet problem. Relations between these principal eigenvalues, their simplicity, and several other properties are further discussed. © 2015 Wiley Periodicals, Inc.     

An analysis of managerialism and performance in English and Welsh male prisons

This paper fills a noticeable gap in the current economic and penology literature by proposing new performance-enhancing policies based on an efficiency analysis of a sample of male prisons in England and Wales over the period 2009/10. In addition, we advance the empirical literature by integrating the managerialism of four strategic functions of prisons, employment and accommodation, capacity utilization, quality of life in prison and the rehabilitation and re-offending of prisoners. We find that by estimating multiple models focussing on these different areas some prisons are more efficient than other establishments. In terms of policy, it is therefore necessary to consider not just an overall performance metric for individual prisons, as currently undertaken annually by the UK Ministry of Justice, but to look into the administration and managerialism of their main functions in both a business and public policy perspective. Indeed, it is further necessary to view prisons together and not as single entities, so as to obtain a best practice frontier for the different operations that management undertakes in English and Welsh prisons.     

Synthesis of side‐chain‐substituted ifosfamide analogs

Three analogs of the cytostatic drug ifosfamide incorporating 1‐methyl‐2‐chloroethyl side chains were designed and prepared as an attempt to obtain drugs of lower toxicity.