Incompletely condensed fluoroalkyl silsesquioxanes and derivatives: precursors for low surface energy materials

A novel synthetic method was developed for the controlled functionalization of fluorinated polyhedral oligomeric silsesquioxanes (F-POSS), which are useful as low surface energy materials for superhydrophobic and superoleophobic materials. Utilizing triflic acid, open-cage compounds were created and then reacted with a variety of dichlorosilanes to produce functional F-POSS structures possessing alkyl-, aryl-, and acrylate-based moieties. The crystal structure for an endo,endo-disilanol F-POSS compound was determined by single-crystal X-ray diffraction. The chemical structures were confirmed using multinuclear NMR spectroscopy ((1)H, (13)C, (19)F, and (29)Si), FT-IR, and combustion analysis. Dynamic contact angle measurements of these compounds were taken with water and hexadecane. These novel structures were found to possess excellent wetting-resistant behavior, similar to that of the parent F-POSS compound. They are the first well-defined fluorinated nano-building blocks with a controlled level of reactive functionality for the development of new superhydrophobic and superoleophobic materials.     

Total synthesis of (±)-cortistatin J from furan

A concise, diastereoselective total synthesis of (±)-cortistatin J has been completed in 20 steps from furan. Key steps include an intramolecular [4 + 3] cyclization of a disubstituted furan with a (Z)-2-(trialkylsilyloxy)-2-enal to construct the tetracyclic core and a (Z)-vinylsilane/iminium ion cyclization to form the A ring.     

White Emitters by Tuning the Excited‐State Intramolecular Proton‐Transfer Fluorescence Emission in 2‐(2′‐Hydroxybenzofuran)benzoxazole Dyes

The synthesis, structural, and photophysical properties of a new series of original dyes based on 2‐(2′‐hydroxybenzofuran)benzoxazole (HBBO) is reported. Upon photoexcitation, these dyes exhibit intense dual fluorescence with contribution from the enol (E*) and the keto (K*) emission, with K* being formed through excited‐state intramolecular proton transfer (ESIPT). We show that the ratio of emission intensity E*/K* can be fine‐tuned by judiciously decorating the molecular core with electron‐donating or ‐attracting substituents. Push–pull dyes 9 and 10 functionalized by a strong donor (nNBu₂) and a strong acceptor group (CF₃ and CN, respectively) exhibit intense dual emission, particularly in apolar solvents such as cyclohexane in which the maximum wavelength of the two bands is the more strongly separated. Moreover, all dyes exhibit strong solid‐state dual emission in a KBr matrix and polymer films with enhanced quantum yields reaching up to 54 %. A wise selection of substituents led to white emission both in solution and in the solid state. Finally, these experimental results were analyzed by time‐dependent density functional theory (TD‐DFT) calculations, which confirm that, on the one hand, only E* and K* emission are present (no rotamer) and, on the other hand, the relative free energies of the two tautomers in the excited state guide the ratio of the E*/K* emission intensities.     

The Use of Solar Radiation by the Photosynthetic Bacterium,Rhodopseudomonas palustris: Model Simulation of Conditions Found in a Shallow Pond or a Flatbed Reactor

Photosynthetic bacteria are attractive for biotechnology because they produce no oxygen and so H₂‐production is not inhibited by oxygen as occurs in oxygenic photoorganisms. Rhodopseudomonas palustris and Afifella marina containing BChl a can use irradiances from violet near‐UV (VNUV) to orange (350–650 nm) light and near‐infrared (NIR) light (762–870 nm). Blue diode‐based pulse amplitude modulation technology was used to measure their photosynthetic electron transport rate (ETR). ETR vs Irradiance curves fitted the waiting‐in‐line model—ETR = (ETR_max × E/E_opt) × exp (1 ? E/E_opt). The equation was integrated over pond depth to calculate ETR of Afifella and Rhodopseudomonas in a pond up to 30 cm deep (A₃₇₆, 1 cm = 0.1). Afifella saturates at low irradiances and so photoinhibition results in very low photosynthesis in a pond. Rhodopseudomonas saturates at ≈15% sunlight and shows photoinhibition in the surface layers of the pond. Total ETR is ≈335 μmol (e^?) m^?2 s^?1 in NUV + photosynthetically active radiation light (350–700 nm). Daily ETR curves saturate at low irradiances and have a square‐wave shape: ≈11–13 mol (e^?) m^?2 day^?1 (350–700 nm). Up to 20–24% of daily 350–700 nm irradiance can be converted into ETR. NIR is absorbed by water and so competes with the bacterial RC‐2 photosystem for photons.     

A Facile Method for Monoesterification of α, ω-Dicarboxylic Acids: Application to the Synthesis of Traumatic Acid,A Prostaglandin Synthon

During the past decade, methyl 7-(5-oxocyclopentenyl)heptanoate (6) has been frequently used as a key intermediate in prostaglandin synthesis.¹ Although keto ester 6 can be readily obtained by treatment of traumatic acid (5) with polyphosphoric acid followed by esterification with methanolic hydrochloric acid,² this approach is not attractive for large-scale synthesis due to the expense of the latter natural product (5). Recently Salomon and Reuter have reported¹ an alternate route to synthon 6 based on a starting material derived from aleuritic acid, a major component of shellac.     

Good and bad market research: A critical review of Net Promoter Score

Net Promoter Score, touted as the “single customer metric you need” and calculated from customers' answer to one simple question about their loyalty, has been in use since 2003 and adopted in a wide variety of settings. However, it has not lived up to its claimed benefits. This article evaluates the NPS approach in terms of its positive and negative results. This article is for people interested in NPS, still considering implementing NPS in their company, or interested in its technical underpinnings. It points out the benefits and shortcomings and explains why, and it describes what can be done to achieve the outcomes NPS theory claimed it would produce, but has not. The article is written in two parts for quite distinct audiences: firstly, for executives and managers who need customer data and information to make marketing decisions; and secondly, for market researchers, statisticians, and business analysts who are responsible for capturing and providing reliable, understandable, and meaningful customer data to the executives and managers who need the information. Consequently, the two sections are written in two different styles. The first section takes the form of a summary for managers and executives of our findings and recommendations in language aimed at business leaders; the second section provides a detailed analysis and critical review of NPS for market researchers, statisticians, and business analysts. Both sections present a better solution than NPS for understanding what customers value, delivering the best value to customers, winning market share, and creating truly loyal customers.     

Synthesis of 6-phenyl and 6-styrylthiazolo[3,2-b] [1,2,4]triazoles

Thiazole rings have been often encountered in the structure of antibiotic or antitumor drugs. An easy synthesis of them has revealed itself necessary in order to elucidate the mechanism of action of these naturally occurring substances. A method of preparation of conjugated b-ethylenic thiazole[3,2-b] [1,2,4]triazoles by heating a 3-thio substituted [1,2,4]triazole in the presence of polyphosphoric acid is reported here, giving the expected product in a 60% yield.