Micro fabrication of microlens arrays by micro dispensing

In this study, master of the microlens arrays is fabricated using micro dispensing technology, and then electroforming technology is employed to replicate the Ni mold insert of the microlens arrays. Finally, micro hot embossing is performed to replicate the molded microlens arrays from the Ni mold insert. The resin material is used as the dispensing material, which is dropped on a glass substrate. The resin is exposed to a 380 W halogen light. It becomes convex under surface tension on the glass substrate. A master for the microlens arrays is then obtained. A 150‐nm‐thick copper layer is sputtered on the master as an electrically conducting layer. The electroforming method replicates the Ni mold insert from the master of the microlens arrays. Finally, micro hot embossing is adopted to replicate the molded microlens arrays. The micro hot embossing experiment employs optical films of polymethylmethacrylate (PMMA) and polycarbonate (PC). The processing parameters of micro hot embossing are processing temperature, embossing pressure, embossing time, and de‐molding temperature. Taguchi's method is applied to optimize the processing parameters of micro hot embossing for molded microlens arrays. An optical microscope and a surface profiler are utilized to measure the surface profile of the master, the Ni mold insert and the molded microlens arrays. AFM is employed to measure the surface roughness of the master, the Ni mold insert and the molded microlens arrays. The sag height and focal length are determined to elucidate the optical characteristics of the molded microlens arrays. Copyright © 2009 John & Sons, Ltd.     

The spectrophotometric study of a fluorescence‐enhanced inclusion complex threaded with β‐cyclodextrin: Synthesis and characterization

A novel achiral monomer end‐capped with a phenyl‐[1,3,4]oxadiazolyl group and threaded through β‐cyclodextrin was synthesized to investigate the host‐guest interactions in the inclusion complex. ¹H NMR studies revealed that one or two cyclodextrin molecules were threaded onto the synthesized achiral monomer, leading to the formation of a fibrous construction of self‐assembled inclusion complexes. The formation of a self‐assembled inclusion complex was identified using SEM and TEM. The highly ordered alignment of self‐assembled supramolecules was confirmed using polarized optical microscopy. We demonstrate an easy process for the fabrication of nano‐structured self‐assembled inclusion complexes in pyridine/ethanol (1 mL/10 mL) as well as the enhancement of photo‐induced fluorescence via monomers end‐capped with a phenyl‐[1,3,4]oxadiazolyl moiety threaded with β‐cyclodextrins. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3368–3374, 2010     

Multielectron Redox Chemistry of a Neutral,NIR‐Active,Indigo‐Pillared ReI‐Based Triangular Metalloprism

Self‐assembled, hexarhenium(I), triangular metalloprism compound [{(CO)₃Re(μ‐ 2 )Re(CO)₃}₃(μ₃‐ 1 )₂] ( 3 ) featuring three bis‐chelating pillarlike indigo dianions (μ‐ 2 ), each of which connects two fac‐Re(CO)₃ cores, which are interconnected by a tritopic N donor, that is, a 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine (μ₃‐ 1 , tPyTz) ligand, has been synthesized in high yield and characterized. Metalloprism 3 exhibits a strong absorption in the near‐infrared (NIR) region. The reversible, multielectron redox properties of the electrogenerated 3 ⁿ species, where n=3+, 0, 3?, 4?, 5?, 8?, in the visible and especially in the NIR region were investigated in THF solution by cyclic voltammetry (CV), chronocoulometry, EPR spectroscopy, and thin‐layer UV/Vis/NIR spectroelectrochemistry (SEC). Stepwise, site‐specific electrochemical reductions lead to the formation of a series of highly stable ion (radical) species in which electrons associated with μ‐ 2 or μ₃‐ 1 components of the molecule can be clearly distinguished. An EPR investigation revealed interaction of unpaired electrons with the metal nuclei (^185,187Re, I=5/2) in the reduced intermediates. The framework has C₂ symmetry, and accidental degeneracies suffice. Detailed theoretical calculations by structure‐based DFT confirm that the triply degenerate HOMO has ≥70 % indigo character with a sizable dπ‐Re character, while the LUMO is dominated by the triply degenerate indigo ligands, and the LUMO+1 by doubly degenerate tPyTz ligands. A comparison of 3 and previously reported 2,2′‐bis‐benzimidazolate‐ (BiBzlm) or alkoxy‐pillared Re^I metalloprisms indicates a very low switching potential with a potential window of less than 1 V and reversibly accessible optical properties with higher stability of the intermediates. The properties exhibited by 3 appear to be due to the slight tuning of the bridging ligand from N,N^? to N,O^?.     

Four‐ and Five‐Coordinate Gallium Complexes Stabilized by Bidentate 2‐(Dimethylaminomethyl)Pyrrole Ligand: Molecular Structures of Ga[NC4H3(CH2NMe2)‐2]3 and GaMe2[NC4H3(CH2NMe2)‐2]

Treatment of GaCl₃ with one equiv of Li[NC₄H₃(CH₂NMe₂)‐2] (n = 1, 2, 3) in diethyl ether at ?78 °C yields GaCl_3‐n[NC₄H₃(CH₂NMe₂)‐2]_n (n = 1, 1 ; n = 2, 2 ; n = 3, 3 ). Compound 1 reacts with two equiv of RLi to afford GaR₂[NC₄H₃(CH₂NMe₂)‐2] ( 4a, R=Me; 4b, R=Bu ) via transmetallation. Reacting 2 with one equiv of RLi in diethyl ether, 3 and 4 are formed via ligand redistribution. Variable temperature ¹H NMR spectroscopic experiments reveal that the five‐coordinate gallium compound 3 is fluxional and results in a coalescence temperature at 5 °C, at which ΔG^≠ is calculated at ca. 10.4 Kcal/mole. All the new compounds have been characterized by ¹H and ¹³C NMR spectroscopy and the structures of compounds 3 and 4a have also been determined by X‐ray crystallography.     

Polymerization of methyl methacrylate by 2‐pyrrolidinone and n‐dodecyl mercaptan

The bulk polymerization of methyl methacrylate initiated with 2‐pyrrolidinone and n‐dodecyl mercaptan (R‐SH) has been explored. This polymerization system showed “living” characteristics; for example, the molecular weight of the resulting polymers increased with reaction time by gel permeation chromatographic analysis. Also, the polymer was characterized by Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR techniques. The polymer end with the iniferter structures was found. By the initial‐rate method, the polymerization rate depended on [2‐pyrrolidinone]^1.0 and [R‐SH]⁰. Combining the structure analysis and the polymerization‐rate expression, a possible mechanism was proposed. n‐Dodecyl mercaptan served dual roles—as a catalyst at low conversion and as a chain‐transfer agent at high conversion. Finally, the thermal properties were studied, and the glass‐transition temperature and thermal‐degradation temperature were, respectively, 25 and 80–100 °C higher than that of the azobisisobutyronitrile system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3692–3702, 2002     

Preparation and Application of Immobilized Fullerene C60‐Heparin for Anticoagulation of Blood

The interaction between fullerene C60 and heparin was studied using a fullerene C60‐coated piezoelectric quartz crystal sensor. The irreversible response of the piezoelectric quartz crystal was found which could be attributed to the quite strong adsorption of heparin onto the C60 molecule. Immobilized fullerene C60‐Heparin was prepared and successfully applied as a good inhibitor for blood clotting. Like solvated heparin, both wet and dry C60‐heparin solid all demonstrated excellent ability of anticoagulation of blood. The blood clotting time with C60‐heparin solid was found to be > 7 days, while only 17.9 min required for blood clotting time in the absence of C60‐heparin solid. Furthermore, the C60‐heparin coated artificial PVC blood vessels were prepared by coating fullerene C60 onto the surface of artificial PVC blood vessels, followed by the adsorption of water solvated heparin onto the fullerene C60 molecule to form C60‐heparin coating. The blood clotting time of blood in artificial PVC blood vessels with C60‐heparin coating was found to be > 30 days, while only ≤ 30 min. of blood clotting time without the C60‐Heparin coating was observed. The C60‐heparin coated artificial PVC blood vessels can be expected to be employed in human body for the anticoagulation of blood.     

Chelating and Tellurolate Ligand‐Transfer Studies of the Complex fac‐[Fe(CO)3(TePh)3]−: Crystal Structures of Heterodinuclear (CO)3Mn(μ‐TePh)3Fe(CO)3 and CpNi(TePh)(PPh3)

Complex fac‐[Fe(CO)₃(TePh)₃]^? was employed as a “metallo chelating” ligand to synthesize the neutral (CO)₃Mn(μ‐TePh)₃Fe(CO)₃ obtained in a one‐step synthesis by treating fac‐[Fe(CO)₃(TePh)₃]^? with fac‐[Mn‐(CO)₃(CH₃CN)₃]⁺. It seems reasonable to conclude that the d⁶ Fe(II) [(CO)₃Fe(TePh)₃]^? fragment is isolobal with the d⁶ Mn(I) [(CO)₃Mn(TePh)₃]^2? fragment in complex (CO)₃Mn(μ‐TePh)₃Fe(CO)₃. Addition of fac‐[Fe(CO)₃(TePh)₃]^? to the CpNi(I)(PPh₃) in THF resulted in formation of the neutral CpNi(TePh)(PPh₃) also obtained from reaction of CpNi(I)(PPh₃) and [Na][TePh] in MeOH. This investigation shows that fac‐[Fe(CO)₃(TePh)₃]^? serves as a tridentate metallo ligand and tellurolate ligand‐transfer reagent. The study also indicated that the fac‐[Fe(CO)₃(SePh)₃]^? may serve as a better tridentate metallo ligand and chalcogenolate ligand‐transfer reagent than fac‐[Fe(CO)₃(TePh)₃]^? in the syntheses of heterometallic chalcogenolate complexes.     

Characterization of Novel Aminobenzylcantharidinimides and Related Imides by Proton NMR Spectra and Their Effects on NO Induction

Various acidic anhydrides including cantharidin were converted into corresponding aminobenzylcantharidinimide 3a and analogous imides 3b～k (at the ortho, meta, and para positions) with 35%～87% yields by reacting with aminobenzylamines and triethylamine. The two methyl side chains of cantharidinimides 3ao , 3am , and 3ap, and related imides had more than two chiral centers; the lone pair of electrons of nitrogen displayed a different chemical shift and coupling constant in H‐NMR spectra when the amino group of benzylamine was in the ortho position. These cantharidinimides had parent aniline, pyridine, and naphthalene plane structures, and the primary amine nucleophilicity and basicity might reflect the inductive electron’s negative effect on chemical shifts. We prepared cantharidinimides by heating the reactants cantharidin 1a , aliphatic and aromatic acid anhydrides, primary benzylic amines, and aniline derivatives to ca. 200 °C with 3 mL of dry toluene, and 1～2 mL of triethylamine in high‐pressure sealed tubes (Buchi glasuster 0032) to produce cantharidinimides and their analogues in good yields. The para‐aminobenzylic imides showed greater inhibition of nitric oxide (NO) synthesis by NO synthase (NOS) than did ortho‐ and meta‐aminobenzylic imides. Compound 3fp , para‐aminobenzylic norbonane‐imide, had the most potent effect on inducible NOS among the tested compounds and showed 35% inhibition.