Synthesis of sugar oxime ether surfactants

A straightforward synthesis of a novel class of sugar surfactants is described. The key step is the chemoselective condensation of a hydrophobic alkoxyamine with the resident aldehyde/ketone moiety on a hydrophilic sugar. Neither protection/deprotection of the sugars nor extensive product purification is required. The method allows for the facile adjustment of hydrophobic and hydrophilic domains of the sugar oxime ether surfactant and uses inexpensive, readily accessible, and renewable materials.     

Nucleophilic Reactivity of a Copper(II)–Superoxide Complex

Metal‐bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen‐activating metalloenzymes. In the nonheme iron α‐ketoglutarate dependent oxygenases and pterin‐dependent hydroxylases, however, Fe^III–superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a Cu^II–superoxide complex ( 1 ) with acyl chloride substrates, we have found that a metal–superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer–Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal–superoxide reactivity. Our observations provide support for the postulated role of metal–superoxide intermediates in nonheme iron α‐ketoglutarate dependent and pterin‐dependent enzymes.     

Water‐Stable Zirconium‐Based Metal–Organic Framework Material with High‐Surface Area and Gas‐Storage Capacities

We designed, synthesized, and characterized a new Zr‐based metal–organic framework material, NU‐1100 , with a pore volume of 1.53 ccg^?1 and Brunauer–Emmett–Teller (BET) surface area of 4020 m²g^?1; to our knowledge, currently the highest published for Zr‐based MOFs. CH₄/CO₂/H₂ adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 g g^?1, which corresponds to 43 g L^?1. The volumetric and gravimetric methane‐storage capacities at 65 bar and 298 K are approximately 180 v_STP/v and 0.27 g g^?1, respectively.     

Simple but Precise Engineering of Functional Nanocapsules through Nanoprecipitation

A general, rapid, and undemanding method to generate at will functional oil‐filled nanocapsules through nanoprecipitation is reported. On the basis of polymer and hexadecane/water/acetone phase diagrams, the composition can be set so that polymer chains preferentially stick at the interface of the oil droplets to create nanocapsules. The nanocapsules can be decorated with biorelevant molecules (biotin, fluorescent tags, metal nanoparticles) within the shell and loaded with hydrophobic molecules in a simple one‐pot procedure.     

Strong and Superhydrophobic Wood with Aligned Cellulose Nanofibers as a Waterproof Structural Material†

Lightweight structural materials are important for the energy efficiency of applications, particularly those in the building sector. Here, inspired by nature, we developed a strong, superhydrophobic, yet lightweight material by simple in situ growth of nano‐SiO₂ and subsequent densification of the wood substrate. In situ generation of SiO₂ nanoparticles both inside the wood channels and on the wood surfaces gives the material superhydrophobicity, with static and dynamic contact angles of 159.4^o and 3^o, respectively. Densification of the wood to remove most of the spaces among the lumen and cell walls results in a laminated, dense structure, with aligned cellulose nanofibers, which in turn contributes to a high mechanical strength up to 384.2 MPa (7‐times higher than natural wood). Such treatment enables the strong and superhydrophobic wood (SH‐Wood) to be stable and have excellent water, acid, and alkaline resistance. The high mechanical strength of SH‐Wood combined with its excellent structural stability in harsh environments, as well its low density, positions the strong and superhydrophobic wood as a promising candidate for strong, lightweight, and durable structural materials that could potentially replace steel.     

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy

Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an Fe^IINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot ³MLCT state, from the initially excited ¹MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the ³MC state, in competition with vibrational relaxation and cooling to the relaxed ³MLCT state. The relaxed ³MLCT state then decays much more slowly (7.6 ps) to the ³MC state. The ³MC state is rapidly (2.2 ps) deactivated to the ground state. The ⁵MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the ³MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance.     

Total Synthesis of (±)‐Phyllantidine: Development and Mechanistic Evaluation of a Ring Expansion for Installation of Embedded Nitrogen‐Oxygen Bonds

The development of a concise total synthesis of (±)‐phyllantidine ( 1 ), a member of the securinega family of alkaloids containing an unusual oxazabicyclo[3.3.1]nonane core, is described. The synthesis employs a unique synthetic strategy featuring the ring expansion of a substituted cyclopentanone to a cyclic hydroxamic acid as a key step that allows facile installation of the embedded nitrogen‐oxygen (N?O) bond. The optimization of this sequence to effect the desired regiochemical outcome and its mechanistic underpinnings were assessed both computationally and experimentally. This synthetic approach also features an early‐stage diastereoselective aldol reaction to assemble the substituted cyclopentanone, a mild reduction of an amide intermediate without N?O bond cleavage, and the rapid assembly of the butenolide found in ( 1 ) via use of the Bestmann ylide.     

Thermal performance of a carbon fiber composite material heat sink in an FC-72 thermosyphon

This study analyzes the use of a carbon fiber epoxy heat sink for evaporator surface enhancement in a FC-72 thermosyphon. The pin-fin heat sink features 945 small-cross-section (1.27 mm by 0.965 mm) fins fabricated with an integral base plate. These fins have a high thermal conductivity (500 W/m K) along the length of the fin. The influence of heat load, thermosyphon fill volume, and condenser operating temperature on the overall thermal performance is examined. The results of this experiment provide significant insight into the possible implementation and potential benefits of carbon-fiber heat sink technology in two-phase flow leading to significant improvements in thermal management strategies for advanced electronics.     

Benefit of modulated maskers for speech recognition by younger and older adults with normal hearing

To assess age-related differences in benefit from masker modulation, younger and older adults with normal hearing but not identical audiograms listened to nonsense syllables in each of two maskers: (1) a steady-state noise shaped to match the long-term spectrum of the speech, and (2) this same noise modulated by a 10-Hz square wave, resulting in an interrupted noise. An additional low-level broadband noise was always present which was shaped to produce equivalent masked thresholds for all subjects. This minimized differences in speech audibility due to differences in quiet thresholds among subjects. An additional goal was to determine if age-related differences in benefit from modulation could be explained by differences in thresholds measured in simultaneous and forward maskers. Accordingly, thresholds for 350-ms pure tones were measured in quiet and in each masker; thresholds for 20-ms signals in forward and simultaneous masking were also measured at selected signal frequencies. To determine if benefit from modulated maskers varied with masker spectrum and to provide a comparison with previous studies, a subgroup of younger subjects also listened in steady-state and interrupted noise that was not spectrally shaped. Articulation index (AI) values were computed and speech-recognition scores were predicted for steady-state and interrupted noise; predicted benefit from modulation was also determined. Masked thresholds of older subjects were slightly higher than those of younger subjects; larger age-related threshold differences were observed for short-duration than for long-duration signals. In steady-state noise, speech recognition for older subjects was poorer than for younger subjects, which was partially attributable to older subjects' slightly higher thresholds in these maskers. In interrupted noise, although predicted benefit was larger for older than younger subjects, scores improved more for younger than for older subjects, particularly at the higher noise level. This may be related to age-related increases in thresholds in steady-state noise and in forward masking, especially at higher frequencies. Benefit of interrupted maskers was larger for unshaped than for speech-shaped noise, consistent with AI predictions.