Stage-frit: A straightforward sub-2 μm nano-liquid chromatography column fabrication for proteomic analysis

In this work we demonstrated a facile method for the fabrication of C18 coordination polymer gel in a capillary, called stage-frit, which was efficiently applied to pack sub-2 μm C18 beads into the capillary by a high pressure bomb for the online separation of proteolytic peptides. The back pressure of the column with 10 cm × 75 μm i.d. is regularly lower than 170 bar at a flow rate of 300 nl/min, which could be operated on a common nanoLC system instead of nanoUPLC system due to the good permeability, low back pressure and high mechanical stress of the frit that will totally reduce the cost for the purchase of instrument. The stage-frit allows long-term continuous flow of the solvent and no significant beads loss or pressure instability was observed during the period. The repeatability of retention time for fifteen BSA tryptic peaks was found to be less than 1.08% (RSD) in six time nanoLC-ESI-MS/MS experiments. The average full width at half maximum (FWHM) of peptide peaks is 5.87 s. The sub-2 μm stage-frit nanoLC column showed better sensitivity than the commercial available for large scale proteomic analysis of total tissue proteins from human spleen. The number of identified peptides is approximately 0.4-fold and 0.2-fold higher than that obtained by utilizing commercial columns packed with 3 μm and 1.8 μm C18 materials, respectively. In the field of analytical chemistry, particularly the use of nanoLC systems, stage-frit nanoLC column offers a great potential for the separation of complex mixtures.     

Direct Synthesis of Chiral 3‐Arylsuccinimides by Rhodium‐Catalyzed Enantioselective Conjugate Addition of Arylboronic Acids to Maleimides

Chiral rhodium catalysts comprising 2,5‐diaryl‐ substituted bicyclo[2.2.1]diene ligands L1 – L10 were utilized in the enantioselective 1,4‐addition reaction of arylboronic acids to N‐substituted maleimides. In the presence of 2.5 mol % of Rh^I/ L2 , enantioenriched conjugate addition adducts were isolated in 72–99 % yields with 86–98 % ee. This protocol offers a convenient method to access a variety of 3‐arylsuccinimides in a highly enantioselective manner. Maleimides with readily cleavable N‐protecting groups were tolerated enabling the synthesis of useful synthetic intermediates. Pyrrolidine 4 , a biologically active compound, and pyrrolidine 5 , an ent‐precursor to an HSD‐1 inhibitor, were synthesized to demonstrate the utility of this method.     

Synthesis of five-coordinate manganese(I) carbonyl complex [(CO)<Subscript>3</Subscript>Mn (-S,-Se-C<Subscript>6</Subscript>H<Subscript>3</Subscript>-4-Me)]<Superscript>−</Superscript>: influences of non-innocent ligand to the structure,reactivity and electrochemical property

Oxidative addition of Br₂ to [Mn(CO)₅]^? leads to the formation of [(CO)₄MnBr], followed by the ligand exchange of bromide to [S,Se-C₆H₃-4-Me] ₂ ^2? to form complex (CO)₃Mn (µ-? ⁴-SC₆H₃-4-(CH₃)Se-SeC₆H₃-4-(CH₃)S)Mn(CO)₃ (1). A new five-coordinate complex [(CO)₃Mn(-S,-Se-C₆H₃-4-CH₃)]^? (2) can be synthesized through two different routes: (a) oxidative addition of diselenide [HS,Se-C₆H₃-4-Me]₂ to the [Mn(CO)₅]^? followed by deprotonation and ligand dissociation to generate complex 2; (b) reduction of diselenide bonds of complex 1 by [BH₄]^? to produce 2. Drop-wise addition of HBF₄·OEt₂ at 0 °C results in the formation of complex 1. The X-ray analysis shows that complex 2 has relative short Mn–Se and Mn–S bond distances compare to the published structures of cis-[(CO)₄Mn(EPh)₂]^? (E = S and Se; Liaw et al. in J. Chin. Chem. Soc. 43:427–431, 1996; Liaw et al. in Inorg. Chem. 35:2530, 1996). Interestingly, exposure of the coordinated unsaturated complex 2 under CO_(g) atmosphere resulted in complex cis-[(CO)₄Mn(-S,-Se-C₆H₃-4-Me)]^? (3) being formed. After purging the solution of complex 3 with N₂, it was reconverted completely back to complex 2; this observation was characterized by FTIR. The cyclic voltammetry scan of complex 2 shows a quasi-reversible redox couple with E _1/2 = ?1.94 V and I _pa/I _pc = 0.68. Ligand [HS, Se-C₆H₃-4-CH₃]₂ and complexes 1 and 2 are all characterized by IR, UV–Vis, NMR, EA and X-ray single crystal diffraction.     

Thermomechanical behavior of underfill/solder mask/substrate interface under thermal cycling

With the increasing application of flip-chip technology in the microelectronics industry, the adhesion strength of interfaces in flip-chip microelectronic structures has become an important issue for manufacturing and operation. In this paper we present an experimental investigation of the adhesive strength of underfill material to solder mask coated FR-4 substrate under thermal cycling. The effects of the number of thermal cycles on interfacial strength were investigated by using the button shear test. The relationship between interfacial strength and the thickness of solder mask was also examined. Furthermore, the morphologies of fracture surfaces of the test specimens were analyzed by scanning electron microscopy. The results of this study show that the interfacial strength of the underfill/solder mask/substrate joint was significantly reduced by thermal fatigue. Finally, the degradation behavior and possible mechanisms were then determined on the basis of these observations.     

On damping coefficient due to phase transformation

The damping coefficient of capillary waves due to the evaporation-condensation process at the interface of the two phases of a fluid is evaluated. To highlight the mechanism of the effect of heat and mass transfer across the interface between regions of liquid and vapor, potential flow of incompressible fluids are assumed. Thus other mechanisms of damping are neglected. To fascilitate the analysis, the method of multiple-scale is employed in the analysis, even though the problem is linear.     

Water waves in an elastic vessel

Linear and nonlinear analyses of water waves in an elastic vessel are carried out to study the dramatic phenomena of Dragon Wash as well as related controllable experiments. It is proposed that the capillary edge waves are generated by parametric resonance, which is shown to be a possible mechanism for both rectangular an circular vessels. For circular vessel, the normal geometric resonance is also operating, thus greatly enhance the dramatic effect. The mechanism of nonlinear mode-mode interaction is proposed for the generation of axisymmetric low-frequency gravity waves by the high- frequency external excitation. A simple model system is studied numerically to demonstrate explicitly this interaction mechanism.     

A study on dose response of NIPAM-based dosimeter used in radiotherapy

The newly manufactured N-isopropylacrylamide (NIPAM) polymer gel is composed of four components, i.e., gelatin, monomer (NIPAM), crosslinker (N,N’-methylenebisacrylamide, Bis), and antioxidant (tetrakis hydroxymethyl phosphonium chloride, THPC). In this study, we investigated the effects of gel composition on the dose response of NIPAM polymer gel. A statistical experiment to analyze the contribution of each composition to the linearity and sensitivity of NIPAM gel was performed. Results indicate that the amount of gelatin, NIPAM (15.17%), Bis, and THPC have dominant effects on the sensitivity of the gel, with contributions of 59.73, 15.17, 10.64, and 14.45%, respectively. The amount of gelatin and Bis mainly affected the linearity of the gel, with contributions of 44.70 and 50.99%, respectively. The linearity of most compositions of the gel was greater than 0.99 when (%C)/(%T) was lower than 8.0. Optimal (%C)/(%T) for higher sensitivity should be in the range of 4−9. The temporal stability experiment showed that the dose response curve attained stability at about 5 h after irradiation and persisted up to 3 months.     

Molecular dynamics simulations of the interfacial and structural properties of dimethyldodecylamine-N-oxide micelles

A series of large-scale atomistic molecular dynamics simulations were conducted to study the structural and interfacial properties of nonionic dimethyldodecylamine-N-oxide (DDAO) micelles with an aggregation number of 104 in pure water, which was determined using small-angle neutron scattering (SANS). From these simulations, the micelles were found to be generally ellipsoidal in shape with axial ratios of ～1.3-1.4, which agrees well with that found from small-angle neutron scattering measurements. The resulting micelles have an area per DDAO molecule of 94.8 ?(2) and an average number of hydration water molecules per DDAO molecule of ～8. The effect of the encapsulation of ethyl butyrate (CH(3)(CH(2))(2)COOCH(2)CH(3), C(4)) and ethyl caprylate (CH(3)(CH(2))(6)COOCH(2)CH(3), C(8)) on the structural and interfacial properties of the nonionic DDAO aggregates was also examined. In the presence of the C(4) oil molecules, the aggregates were found to be less ellipsoidal and more spherical than the pure DDAO micelles, while the aggregates in the presence of the C(8) oil molecules were almost perfect spheres. In addition, the C(4) oil molecules move into the core of the aggregates, while the C(8) oil molecules stay in the headgroup region of the aggregates. Finally, the structural properties of two micelles formed from different starting states (a "preassembled" sphere and individual DDAO molecules distributing in water) were found to be nearly identical.     

Optical and structural characteristics of yttrium doped ZnO films using sol–gel technology

Yttrium-doped ZnO gel was spin-coated on the SiO₂/Si substrate. The as-prepared ZnO:Y (YZO) thin films then underwent a rapid thermal annealing (RTA) process conducted at various temperatures. The structural and photoluminescence characteristics of the YZO films were discussed thereafter. Our results indicated that the grain size of YZO thin films being treated with various annealing temperatures became smaller as compared to the ones without being doped with yttrium. Furthermore, unlike other ZnO films, the grains of YZO thin films appeared to separate from one another rather than aggregating together as both types of the films were annealed under the same environment. The photoluminescence characteristic measured showed that the UV emission was the only radiation obtained. However, the UV emission intensity of YZO thin film was much stronger than that of the ZnO thin film after annealing them with the same condition. It was also found that the intensity increased with an increase in the annealing temperature, which was caused by the exciton generated and the texture surface of the YZO thin film.     

Far-infrared radiation promotes angiogenesis in human microvascular endothelial cells via extracellular signal-regulated kinase activation

This study was designed to determine the in vitro angiogenic ability of far-infrared (FIR) radiation in the skin-derived cultured human microvascular endothelial cells and to elucidate the role of mitogen-activated protein kinases (MAPKs) in this process. The results revealed that FIR radiation from a WS(TM) TY301 FIR emitter activated p38 and extracellular signal-regulated kinase (ERK), but not Akt or c-Jun N-terminal protein kinases (JNK), and significantly promoted angiogenesis by increasing tube formation in Matrigel and the migration of cells across an eight micron polyester filter. The addition of 50 μM PD98059, a MEK inhibitor, significantly inhibited the activation of ERK and the enhanced angiogenesis; in contrast, the inhibition of p38 phosphorylation did not inhibit the enhanced angiogenesis. After FIR radiation, there was no increase in vascular endothelial growth factor (VEGF) isoforms (VEGF-A, -B, -C and -D) mRNA and VEGF protein, no increase phosphorylation of endothelial nitric oxide synthase (eNOS) detected using Western blotting, and no increase in NO production detected using flow cytometry in cells pre-incubated with the cell-permeable NO-binding dye diluted 4-amino-5-methylamino-2', 7'-difluorofluorescein diacetate (DAF-FM DA). This study revealed that FIR radiation possesses in vitro angiogenic activity via the activation of the MEK/ERK but not the VEGF/Akt/eNOS-dependent signaling pathways.