A simple polysilsesquioxane sealing of nanofluidic channels below 10 nm at room temperature

We present a simple sealing method to fabricate nanofluidic channels, where plasma treated polysilsesquioxane (PSQ) thin film on a rigid support is used to bond to a hydrophilic glass surface permanently at room temperature. This method shows precise dimension control below 10 nm with easy experimental setup. Using this method, one dimensional confined shallow nanochannels with a depth as small as 8 nm and an aspect ratio of <4 x 10(-5), two dimensional confined nanochannel arrays, and integrated nano/microchannel devices with a micro-to-nano interface have been demonstrated. Smooth transfer of DNA fragments from microchannel to nanochannel through the interface area was observed.     

Iridium(I) pyridyl azolate complexes with saturated red metal-to-ligand charge transfer phosphorescence; fundamental and potential applications in organic light-emitting diodes

Preparation of a new series of neutral metal complexes [(cod)Ir(fppz)] (1), [(cod)Ir(bppz)] (2), [(cod)Ir(fptz)] (3) and [(cod)Ir(bptz)] (4), bearing one cod ligand and a pyridyl azolate chelate are reported. A single-crystal X-ray diffraction study of 3 reveals the expected distorted square-planar geometry. The lowest absorption band consists of IrI atom increased triplet dpi-->pi* transitions (3MLCT), the assignment of which is firmly supported by the theoretical approaches. Complexes 1-4 exhibit weak phosphorescence in degassed solution at room temperature, whereas much more intense, solid-state phosphorescence appears in the range 622-649 nm. The pure MLCT emission was used as a prototypical model to address its remarkable spectral differences from the IrIII isoquinoline pyrrolide complex (5), which has mainly 3pipi phosphorescence. Complex 3 was used as a dopant to fabricate red-emitting phosphorescent organic light-emitting diodes (OLEDs). For the 7 % doped device, a maximum brightness of 3010 cd m-2 was achieved at an applied voltage of 15 V and with CIE coordinates of (0.56, 0.33), demonstrating for the first time the potential of neutral IrI complexes in OLED applications.     

Color tuning associated with heteroleptic cyclometalated Ir(III) complexes: influence of the ancillary ligand

We report the preparation of a series of new heteroleptic Ir(III) metal complexes chelated by two cyclometalated 1-(2,4-difluorophenyl)pyrazole ligands (dfpz)H and a third ancillary bidentate ligand (L=X). Such an intricate design lies in a core concept that the cyclometalated dfpz ligands always warrant a greater pi pi* gap in these series of iridium complexes. Accordingly, the lowest one-electron excitation would accommodate the pi* orbital of the ancillary L=X ligands, the functionalization of which is then exploited to fine-tune the phosphorescent emission wavelengths. Amongst the L=X ligands designed, three classes (series 1-3) can be categorized, and remarkable bathochromic shifts of phosphorescence were observed by (i) replacing the 2-benzoxazol-2-yl substituent (1a) with the 2-benzothiazol-2-yl group (1b) in the phenolate complexes, (ii) converting the pyridyl group (2a) to the pyrazolyl group (2b) and even to the isoquinolyl group (2c) in the pyrazolate complexes and (iii) extending the pi-conjugation of the benzimidazolate ligand from 3a to 3b. Single-crystal X-ray diffraction study on complex [(dfpz)Ir(bzpz)] (2b) was conducted to confirm their general molecular architectures. Complex 2b was also used as a representative example for fabrication of multilayered, green-emitting phosphorescent OLEDs using the direct thermal evaporation technique.     

Polybenzoxazine as a mold-release agent for nanoimprint lithography

One of the most important tasks remaining to be resolved in nanoimprint lithography is the elimination of the resist sticking to the mold during demolding. Previously, the main approach was to apply a thin layer of fluorinated alkyl silane mold-release agent on the surface on the mold; however, this involves complicated steps and high costs. The low surface free energy material polybenzoxazine provides an efficient mold-release agent for silicon molds that is easier to process, costs less, and has no side reactions.     

Isomerization reactions of RSNO (R=H,C<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>H<Subscript>2<Emphasis Type="Italic">n</Emphasis>+1</Subscript><Emphasis Type="Italic">n</Emphasis>≤ 4)

We have applied various theoretical methods to gain detailed insights into the isomers as well as the transition states (TSs) along the corresponding reaction pathways for RSNO (R=H, C _n H_2n+1 n ≤ 4). On the basis of G2 and G2MP2 results, the relative order of stability for R=H is estimated to be trans-HSNO > cis-HSNO > HNSO > cis-HONS trans-HONS, while it is cis-CH₃SNO trans-CH₃SNO > CH₃NSO > trans-CH₃ONS > cis-CH₃ONS for R=CH₃. A similar trend is also obtained from the B3P86 method with considerably less computing effort if the nearly isoenergetic isomers cis-HONS and trans-HONS are ignored. Based on the results of B3P86, cis-RSNO is more stable than trans-RSNO when R=H is replaced by alkyl groups except for R=t-Bu. Natural bond orbital analyses allow us to explore whether the high reactivity of S-nitrosothiols is due to the strong negative hyperconjugation (). The mesomeric effect of S-nitrosothiols, although non-negligible, does not cause the breakage of N–O bond due to the compensation of columbic attraction between N and O.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Collision dynamics of high-speed droplets upon layers of variable thickness

The collision dynamics between a droplet and a film has been studied with high-impact energy that can be grouped in a dimensionless Weber number, We, as normalized by surface energy. To accomplish this, we have developed a technique based on cutting of a high-speed jet, which can generate a single droplet with speed up to 23 m/s and We on the order of thousands. It was found that the boundaries indicating the occurrence of a central jet and that of a secondary droplet disintegrated from the jet decreased monotonically with increased dimensionless film thickness, H, and remained constant when the film thickness was larger than the crater depth. However, the transition designating multiple droplets that are originated from a central jet shows a non-monotonic trend with the variation of H, with a minimum We being at H ≈ 3, which is about the maximum crater depth, owing to a tuning behavior. The critical We for splashing that occurs at an early phase immediately after the impact is relatively sensitive to the film thickness only when H is between 1 and 2, which increases with reduced H. At large We (≳2,570 for high H), the ejected crown is closed to form a bubble and the transition boundary reveals a similar dependence on H as that for creation of a central jet.     

Mixing of cohesive particles in a shear cell

This paper discusses two series of experiments performed in a shear cell device with six different amounts of silicone oils and using 2-mm soda lime beads as the granular materials. The first series of experiments were mixing experiments, and the developments of mixing layer thicknesses were measured. The second series of experiments had the same experimental conditions as the first series but used different combinations of colored particles. In the second series of experiments, the motions of granular materials were recorded by a high-speed camera. Using the image processing technology and particle tracking method, the positions and velocities of particles were measured. The self-diffusion coefficient could be found from the history of the particle displacements.     

C2, Symmetric Dibenzosuberanes as Templates for the Chirality Determination of Helicenes and Their Applications as Optically Switchable Memory Device

We have recently developed a new type of chiral templates, dibenzosuberanes. Thess C₂, symmetric diaryl modifiers have been successfully applied to the synthesis of chiral triarylcarbenium ions. They can serve as catalysts in the asymmetric Mukaiyama aldol reactions with moderate enantioselectivities of up to 50% [1]. We have subsequently found that one major side reaction between the catalyst and the substrate-silyl ketene acetal which releases extra silyl-X species is responsible for the erosion of asymmetric induction. The dibenzosuberane scaffold was found essential to prevent this type of side reaction. For the selection of carbenium counter ions, we have resorted to the chloride in order to completely suppress the undesired silyl catalysis [2].