Laser Spectroscopy on the MgH A2Π - X2Σ+ Band System

The A²Π - X²Σ⁺ electronic transition of MgH has been studied by the laser excitation spectroscopy. Some new transitions have been observed for the first time. Rotational parameters of the X and A state have been derived and compared with other experimental values.     

Study of a thermotropic liquid-crystalline polyester at elevated pressures

A thermotropic liquid-crystalline copolyester of 20% hydroxybenzoic acid, 40% isophthalic acid, and 40% hydroquinone polymer was studied at elevated pressures. The characterization techniques at elevated pressures (0–1000 bar) included high-pressure differential thermal analysis and dilatometry; at atmospheric pressure, differential scanning calorimetry, thermal optical analysis, and x-ray analysis were employed. The mechanical properties of the solid specimens prepared at different pressures were studied by compression and dynamic rotation mechanical testing techniques. High-pressure induced a new crystal habit in the solid state and a new mesophase in the melt. These transitions are summarized in a proposed phase diagram. Mechanical tests on the material produced at elevated pressure indicate the possibility of improved properties, implying that the pressure-dependent morphological changes in thermotropic copolyesters could be of practical significance. The finding of a pressure-induced mesophase also confirmed the possibility of extending the range of polymers which might exhibit liquid crystallinity via the application of pressure.     

Silver‐Assisted Chemical Etching on Silicon with Polyvinylpyrrolidone‐Mediated Formation of Silver Dendrites

Metal‐assisted chemical etching (MaCE) on silicon (Si)—mediated by polyvinylpyrrolidone (PVP)—is systematically investigated herein. It is found that the morphologies and crystallographic natures of the grown silver (Ag) dendrites can be significantly modulated, with the presence of PVP in the MaCE process leading to the formation of faceted Ag dendrites preferentially along the (111) crystallographic phase, rather than along the (200) phase. Further explorations of the PVP‐mediated effect on Si etching are also revealed. In contrast to the aligned Si nanowires formed by MaCE without PVP addition, only distributed nanopores with sizes of 200 to 400 nm appear on the Si surfaces in the presence of PVP. The origin of surface polishing on Si in the PVP‐mediated MaCE process can be attributed to the distinct transport pathway of holes supplied by the Ag⁺ ions, where the holes are injected directly into the primary Ag seeds, rather than through Ag dendrites, thus leading to the isotropic etching of the Si surface.     

Ortho‐Quinone Methides as Reactive Intermediates in Asymmetric Brønsted Acid Catalyzed Cycloadditions with Unactivated Alkenes by Exclusive Activation of the Electrophile

An efficient method for the highly enantioselective synthesis of chiral chromanes bearing multiple stereogenic centers was developed. A chiral BINOL‐based N‐triflylphosphoramide proved to be an effective catalyst for the in situ generation of ortho‐quinone methides (o‐QMs) and their subsequent cycloaddition reaction with unactivated alkenes provided chromanes with excellent diastereo‐ and enantioselectivity.     

Large Scale Production of Continuous Hydrogel Fibers with Anisotropic Swelling Behavior by Dynamic‐Crosslinking‐Spinning

Hydrogel microfibers have been considered as a potential biomaterial to spatiotemporally biomimic 1D native tissues such as nerves and muscles which are always assembled hierarchically and have anisotropic response to external stimuli. To produce facile hydrogel microfibers in a mathematical manner, a novel dynamic‐crosslinking‐spinning (DCS) method is demonstrated for direct fabrication of size‐controllable fibers from poly(ethylene glycol diacrylate) oligomer in large scale, without microfluidic template and in a biofriendly environment. The diameter of fibers can be precisely controlled by adjusting the spinning parameters. Anisotropic swelling property is also dependent on inhomogeneous structure generated in spinning process. Comparing with bulk hydrogels, the resulting fibers exhibit superior rapid water adsorption property, which can be attributed to the large surface area/volume ratio of fiber. This novel DCS method is one‐step technology suitable for large‐scale production of anisotropic hydrogel fibers which has a promising application in the area such as biomaterials.

     

Comprehensive molecular imaging of photolabile surface samples with synchronized dual-polarity time-of-flight mass spectrometry

This work presents the unique features of a novel configuration of a synchronized dual-polarity time-of-flight mass spectrometer for comprehensive surface imaging. Mass spectrometry imaging of surface samples covering positive and negative ion modes is difficult due to rapid signal depletion. This limitation is overcome here by dual-polarity time-of-flight mass spectrometry (DP-TOFMS) via two separate TOF mass analyzers that are installed above a sample surface. The new instrument eliminates the polarity bias characteristic of most mass spectrometers, which is important for the analysis of samples with diverse physical and chemical properties. The experimental results show for the first time that the spatial distribution of positive and negative ions of various photolabile samples can be distinguished, including pigments and conventional matrix-assisted laser desorption/ionization samples. The different positive and negative ion distributions suggest that accurate quantitative information can only be obtained when the entire sample region is examined by DP-TOFMS, which was unfeasible in the past. Such a comprehensive diagnostic method is essential for the molecular imaging of trace compositions in delicate biological tissues, as demonstrated here with a Phyllanthus urinaria leaf that only produced ion signals in the first examination and not in the subsequent measurements.     

Green microfluidic devices made of corn proteins

An alternative green microfluidic device made of zein, a prolamin of corn, can be utilized as a disposable environmentally friendly microchip especially in agriculture applications. Using standard soft lithography and stereo lithography techniques, we fabricated thin zein films with microfluidic chambers and channels. These were bonded to both a glass slide and another zein film. The zein film with microfluidic features bonds irreversibly with other surfaces by vapor-deposition of ethanol to create an adhesive layer resulting in very little or no trapped air and small shape distortion. Zein-zein and zein-glass microfluidic devices demonstrated sufficient strength to facilitate fluid flow in a complex microfluidic design that showed no leakage under high hydraulic pressure. Zein-glass microfluidic devices with serpentine mixing design showed successful fluid manipulation as a concentration gradient of Rhodamine B solution was generated. The ease of fabrication and bonding and the flexibility and moldability of zein offer attractive possibilities for microfluidic device design and manufacturing. These devices can include several unit operations with mixing being one of the most commonly used. The zein-based microfluidic devices, made entirely from a biopolymer from agricultural origin, offer alternative environmentally friendly material choices that are less dependent on limited petroleum based polymer resources.     

Transimination reactions in [b-3C-im][NTf2] ionic liquid

Compared to conventional molecular solvents, the ionic liquid [b-3C-im][NTf(2)] was found to promote transimination reactions with up to ～100-fold rate enhancement. This rate effect observed at ambient temperature might be explained by the fact that the ionic liquid displays weak Lewis acidity with very low, if any, nucleophilicity and its imidazolium cation is expected to interact by associating with, and thus electrophilically activating, the C=N bond of the starting imine, leading to increased stabilization of the polar, charged intermediate species and ultimately, rapid product formation. Moreover, the presence of 1 mol% Sc(OTf)(3) in [b-3C-im][NTf(2)] further facilitates the transimination reactions studied.     

High-throughput 3D spheroid culture and drug testing using a 384 hanging drop array

Culture of cells as three-dimensional (3D) aggregates can enhance in vitro tests for basic biological research as well as for therapeutics development. Such 3D culture models, however, are often more complicated, cumbersome, and expensive than two-dimensional (2D) cultures. This paper describes a 384-well format hanging drop culture plate that makes spheroid formation, culture, and subsequent drug testing on the obtained 3D cellular constructs as straightforward to perform and adapt to existing high-throughput screening (HTS) instruments as conventional 2D cultures. Using this platform, we show that drugs with different modes of action produce distinct responses in the physiological 3D cell spheroids compared to conventional 2D cell monolayers. Specifically, the anticancer drug 5-fluorouracil (5-FU) has higher anti-proliferative effects on 2D cultures whereas the hypoxia activated drug commonly referred to as tirapazamine (TPZ) are more effective against 3D cultures. The multiplexed 3D hanging drop culture and testing plate provides an efficient way to obtain biological insights that are often lost in 2D platforms.