Lanthanum trilactate: Vibrational spectroscopic study − infrared/Raman spectroscopy

In this study lanthanum trilactate was prepared by neutralization reaction of lactic acid and lanthanum oxide, purified and identified by X-ray powder diffraction. Infrared spectra (Mid-IR region 4000–650 cm⁻¹) and Raman spectra (Stokes region 4000–100 cm⁻¹) of the high quality crystalline samples have been recorded and presented for the first time. For comparison DFT calculations were performed using Gaussian 09 D.01 and agreement between predicted and measured spectral data has been achieved. Acquired information can be utilized for substance identification for example in various industrial applications or in biological systems.     

Redox‐Active NOx Ligands in Palladium‐Mediated Processes

This Minireview highlights the redox and non‐innocent behavior of NO_x ligands (x=1, 2, or 3) in selected Pd‐mediated processes, for example, alkene and aromatic oxidation processes. A focus is placed on mechanistic understanding and linking recent transformations, such as C? H bond activation/functionalization and Wacker oxidation, with previous work on the functionalization of aromatics and alkenes by Pd^II salts.     

Extraordinary transport behavior of gases in isothermally annealed poly(4‐methyl‐1‐pentene) membranes

Poly(4‐methyl‐1‐pentene) (PMP) membranes were modified through isothermal annealing to investigate the change of their crystalline structure and rigid and mobile amorphous fractions (RAF and MAF), assuming a three‐phase model, affected the gas transport behavior. The crystalline structure was characterized by wide‐angle X‐ray diffraction (WAXD) and small‐angle X‐ray scattering (SAXS) techniques, and the free volume properties were analyzed by positron annihilation lifetime spectroscopy. Compared with the pristine membrane, the annealed membranes show higher crystallinity; the crystals undergo partial structural change from form III to form I. The lamellar crystal thickness, rigid amorphous fraction thickness, and long period in the lamellar stacks increase with crystallinity. The annealed PMP membranes exhibit higher permeability due to the increase in larger size free volumes in MAF and higher selectivity due to the increase in smaller size free volumes in RAF, respectively. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2368–2376     

Radical Cyclisation of α‐Halo Aluminium Acetals: A Mechanistic Study

α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature ¹³C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al₂O₂ ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences.     

(3S,4S)-4-氨基-3-羟基-6-甲基庚酸的合成

价廉易得的L-亮氨酸先以苄基同时保护氨基及羧基得(S)-2-(二苄胺基)-4-甲基戊酸苄酯,进而在碱性条件下与乙腈发生亲核取代反应得(S)-4-(二苄胺基)-6-甲基-3-氧代庚腈,再经硼氢化钠选择性还原羰基得(3S,4S)-4-(二苄胺基)-3-羟基-6-甲基庚腈,用双氧水氧化得(3S,4S)-4-(二苄胺基)-3-羟基-6-甲基庚酸,最后在Pd(OH)2/C-H2作用下脱掉苄基得到(3S,4S)-4-氨基-3-羟基-6-甲基庚酸,即(3S,4S)-statine。整个合成路线总产率为33.6%。     

Solar Thermal Energy Storage in a Photochromic Macrocycle

The conversion and efficient storage of solar energy is recognized to hold significant potential with regard to future energy solutions. Molecular solar thermal batteries based on photochromic systems exemplify one possible technology able to harness and apply this potential. Herein is described the synthesis of a macrocycle based on a dimer of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermal couple. By taking advantage of conformational strain, this DHA–DHA macrocycle presents an improved ability to absorb and store incident light energy in chemical bonds (VHF–VHF). A stepwise energy release over two sequential ring‐closing reactions (VHF→DHA) combines the advantages of an initially fast discharge, hypothetically addressing immediate energy consumption needs, followed by a slow process for consistent, long‐term use. This exemplifies another step forward in the molecular engineering and design of functional organic materials towards solar thermal energy storage and release.     

Temperature‐dependent phase‐segregation behavior and antifouling performance of UV‐curable methacrylated PDMS/PEG coatings

Controllable phase segregation adjustment for immiscible polymer blends has always been tough, which hinders the development of amphiphilic antifouling coatings from more accessible blends. Herein, methacrylated poly(dimethylsiloxane) (PDMS‐MA) was synthesized and mixed with poly(ethylene glycol)methylether methacrylate (PEG‐MA). It was interestingly discovered that these PDMS‐MA/PEG‐MA blends displayed upper critical solution temperatures (UCST) due to thermo‐induced conformational change of PEG‐MA and the UCST changed with PDMS‐MA/PEG‐MA mass ratios. Micro‐/nano‐phase segregation, nanophase segregation, or homogenous morphology were therefore achieved. These PDMS‐MA/PEG‐MA blends with different mass ratios were UV‐cured under varying temperatures to fabricate coatings. Their surface morphology and wettability are readily adjusted by phase segregation. For the first time, highly hydrophilic surface was achieved for coatings with microphase segregation because of the exposure of PEG‐rich domains, which exhibited an enhanced protein resistance against bovine serum albumin (BSA). Anti‐bacterial performance (Shewanella loihica) was also observed for these PDMS/PEG coatings. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1612–1623     

TiO2 photocatalysis for the degradation of pollutants in gas phase: From morphological design to plasmonic enhancement

TiO₂-based photocatalysis has become a viable technology in various application fields such as (waste)water purification, photovoltaics/artificial photosynthesis, environmentally friendly organic synthesis and remediation of air pollution. Because of the increasing impact of bad air quality worldwide, this review focuses on the use and optimization of TiO₂-based photocatalysts for gas phase applications. Over the past years various specific aspects of TiO₂ photocatalysis have been reviewed individually. The intent of this review is to offer a broad tutorial on (recent) trends in TiO₂ photocatalyst modification for the intensification of photocatalytic air treatment. After briefly introducing the fundamentals of photocatalysis, TiO₂ photocatalyst modification is discussed both on a morphological and an electronic level from the perspective of gas phase applications. The main focus is laid on recent developments, but also possible opportunities to the field. This review is intended as a solid introduction for researchers new to the field, as well as a summarizing update for established investigators.