Influence of the Auxiliary Acceptor on the Absorption Response and Photovoltaic Performance of Dye‐Sensitized Solar Cells

Three new dyes with a 2‐(1,1‐dicyanomethylene)rhodanine (IDR‐ I , ‐ II , ‐ III ) electron acceptor as anchor were synthesized and applied to dye‐sensitized solar cells. We varied the bridging molecule to fine tune the electronic and optical properties of the dyes. It was demonstrated that incorporation of auxiliary acceptors effectively increased the molar extinction coefficient and extended the absorption spectra to the near‐infrared (NIR) region. Introduction of 2,1,3‐benzothiadiazole (BTD) improved the performance by nearly 50 %. The best performance of the dye‐sensitized solar cells (DSSCs) based on IDR‐ II reached 8.53 % (short‐circuit current density (J_sc)=16.73 mA cm^?2, open‐circuit voltage (V_oc)=0.71 V, fill factor (FF)=71.26 %) at AM 1.5 simulated sunlight. However, substitution of BTD with a group that featured the more strongly electron‐withdrawing thiadiazolo[3,4‐c]pyridine (PT) had a negative effect on the photovoltaic performance, in which IDR‐ III ‐based DSSCs showed the lowest efficiency of 4.02 %. We speculate that the stronger auxiliary acceptor acts as an electron trap, which might result in fast combination or hamper the electron transfer from donor to acceptor. This inference was confirmed by electrical impedance analysis and theoretical computations. Theoretical analysis indicates that the LUMO of IDR‐ III is mainly localized at the central acceptor group owing to its strong electron‐withdrawing character, which might in turn trap the electron or hamper the electron transfer from donor to acceptor, thereby finally decreasing the efficiency of electron injection into a TiO₂ semiconductor. This result inspired us to select moderated auxiliary acceptors to improve the performance in our further study.     

Insulin Surface Acoustic Wave Immunosensor Based on Immobilized C60/Anti‐Insulin Antibody

Immobilized fullerene C₆₀/anti‐insulin antibody was prepared and applied in shear horizontal surface acoustic wave (SH‐SAW) immunosensors to detect insulin in aqueous solutions. The immobilizations of anti‐insulin onto fullerene were studied through a C₆₀/PVC coated SH‐SAW sensor system in liquid. The partially irreversible frequency response for an anti‐insulin antibody was observed by the desorption study, which implied that fullerene could chemically react with anti‐insulin. C₆₀/anti‐insulin coating materials were successfully prepared and identified with an FTIR spectrometer. The C₆₀/anti‐insulin coated SH‐SAW immunosensors were developed and applied for detection of insulin in aqueous solutions. Within the range of normal human insulin concentration, the SH‐SAW immunosensors immobilized with C₆₀/anti‐insulin exhibited linear frequency responses to the concentration of insulin with a sensitivity of 130 Hz/pM. The SH‐SAW immunosensor immobilized with C₆₀/anti‐insulin showed a detection limit of 0.58 pM for insulin in aqueous solution. The interference of various common bio‐species in human blood, e.g. urea, ascorbic acid, tyrosine, and metal ions, to the SH‐SAW immunosensor immobilized with C₆₀/anti‐insulin for insulin was investigated. These common bio‐species interferences showed nearly no interference to the SAW immunosensors coated with C₆₀/anti‐insulin. The reproducibility of the SH‐SAW immunosensor immobilized with C₆₀/anti‐insulin for insulin was also investigated and is discussed.     

Two-color electrophoretic immunoassay for simultaneous measurement of insulin and glucagon content in islets of Langerhans

A multianalyte CE competitive immunoassay using two-color detection was developed to measure insulin and glucagon in islets of Langerhans. Insulin was quantified with FITC-insulin (Ins*) and anti-insulin antibodies (Ins Ab) and glucagon was quantified with Cy5-glucagon (Glu*) and anti-glucagon antibodies (Glu Ab). A 3 mW Ar(+) laser at 488 nm and a 25 mW laser diode at 635 nm were used to excite FITC and Cy5, respectively. Fluorescence was split with a half-silvered mirror and passed through a 520 +/- 20 nm bandpass filter or a 663 nm longpass filter for the detection of insulin and glucagon, respectively. The two-color detection format enabled independent quantitation of both analytes even with concentrations of insulin immunoassay reagents 20-fold higher than glucagon reagents. Simultaneous calibration curves were generated and used to determine insulin and glucagon content in islets of Langerhans. Amounts of insulin and glucagon were 56.6 +/- 3.2 and 1.0 +/- 0.5 ng/islet, respectively. LODs were 7 nM insulin and 3 nM glucagon. The assay will be applicable to fast monitoring of multiple peptides secreted from islets of Langerhans and can be applied to other systems for the quantitation of multiple analytes with large differences in concentrations.     

Design, synthesis and hypoglycemic activity of 3-methyl-1-phenyl-4-{4-[(5-methyl-2-phenyloxazol-4-yl)methoxy]benzylene(benzyl)}-2-pyrazol-5-one

Based on the SAR (structure activity relationship) of TZDs (thiazolidinediones), 3-methyl-1-phenyl-2-pyrazoline-5-one was selected as a substitute for TZD. Compounds of 3-methyl-1-phenyl-4-{4-[(5-methyl-2-phenyloxazol-4-yl)methoxy]benzylene(benzyl)}-2-pyrazol-5-one were designed and synthesized to find some more hypoglycemic active agents and further investigate the SAR of this class of compounds. Butanedione monoxime reacted with (substituted) benzaldehyde via cyclization and chlorination to give 4-(chloromethyl)-5-methyl-2-phenyloxazole derivatives, which condensed with 4-hydroxybenzaldehyde or vanillin, and was followed by the Knoevenagel reaction with 3-methyl-1-phenyl-2-pyrazol-5-one to give compounds Ia-Ih. Compounds Ia-Ih were hydrogenated with Pd-C to give IIa-IIh, and their hypoglycemic activity was evaluated with a glucose oxidase kit and insulin load test on normal mice. Sixteen new target compounds were synthesized. All the compounds were characterized by ¹H NMR, IR, MS and elemental analysis. The preliminary pharmacological tests show that the compounds have good hypoglycemic activity and can enhance the action of insulin, especially Ib, Id and If. __________ Translated from Chemical Journal of Chinese Universities, 2007, 28(4): 672–677 [译自: 高等学校化学学报]     

Development of Prototype Wireless Transmission Measurement for Glucose in Subcutaneous and Brain Striatum

Monitoring of glucose in subcutaneous and brain striatum have been extensively studied in the past. While biocompatibility was one of the limitations, others included the messy measuring equipments preclude monitoring in a complex environment. This study tried to establish an amperometric measurement of glucose in pre‐ and post‐insulin‐administration on diabetic and hyperglycemia rats via wireless. The results have indicated that the wireless sensing kit used was capable of monitoring glucose in both subcutaneous and brain. The physiological data have also shown a new insight on the fabrication of implantable glucose sensors.     

A Highly Sensitive Sandwich Enzyme Immunoassay for Insulin in Human Serum Developed Using Capybara Anti-Insulin Fab' -Horseradish Peroxidase Conjugate

Abstract

A highly sensitive sandwich enzyme immunoassay for insulin in human serum has been developed using capybara anti-insulin serum. Capybara anti-insulin IgG-coated polystyrene balls were incubated with serum samples in the presence of 0.4 M NaCl and then with capybara anti-insulin Fab'-horseradish peroxidase conjugate.

The peroxidase activity bound to the polystyrene balls was correlated to the amount of insulin to be assayed. Serum interference was eliminated by the presence of 0.4 M NaC1, and there was no need to add insulin-free serum to a standard curve. The sensitivity was 4 nU/tube or 0.2 μU/ml of serum when 20 μ1 of serum samples was used. The recovery of insulin added to human serum was 92–97 %. The coefficients of within-assay and between-assay variations were 5.1–7.2 % and 7.6–9.2 %, respectively. The regression equation and correlation coefficient to radioimmunoassay were Y(EIA)=0.91×(RIA)-2.4 and 0.97 (n=76), respectively.     

Molecular Design of D‐π‐A Type II Organic Sensitizers for Dye Sensitized Solar Cells

Four new type II organic dyes with D‐π‐A structure (donor‐π‐conjugated‐acceptor) and two typical type II sensitizers based on catechol as reference dyes are synthesized and applied in dye sensitized solar cells (DSCs). The four dyes can be adsorbed on TiO₂ through hydroxyl group directly. Electron injection can occur not only through the anchoring group (hydroxyl group) but also through the electron‐withdrawing group (? CN) located close to the semiconductor surface. Experimental results show that the type II sensitizers with a D‐π‐A system obviously outperform the typical type II sensitizers providing much higher conversion efficiency due to the strong electronic push‐pull effect. Among these dyes, LS223 gives the best solar energy conversion efficiency of 3.6%, with J_sc=7.3 mA·cm^?2, V_oc=0.69 V, FF=0.71, the maximum IPCE value reaches 74.9%.     

Development and characterization of new insulin containing polysaccharide nanoparticles

A nanoparticle insulin delivery system was prepared by complexation of dextran sulfate and chitosan in aqueous solution. Parameters of the formulation such as the final mass of polysaccharides, the mass ratio of the two polysaccharides, pH of polysaccharides solution, and insulin theorical loading were identified as the modulating factors of nanoparticle physical properties. Particles with a mean diameter of 500 nm and a zeta potential of approximately −15 mV were produced under optimal conditions of DS:chitosan mass ratio of 1.5:1 at pH 4.8. Nanoparticles showed spherical shape, uniform size and good shelf-life stability. Polysaccharides complexation was confirmed by differential scanning calorimetry and Fourier transformed infra-red spectroscopy. An association efficiency of 85% was obtained. Insulin release at pH below 5.2 was almost prevented up to 24 h and at pH 6.8 the release was characterized by a controlled profile. This suggests that release of insulin is ruled by a dissociation mechanism and DS/chitosan nanoparticles are pH-sensitive delivery systems. Furthermore, the released insulin entirely maintained its immunogenic bioactivity evaluated by ELISA, confirming that this new formulation shows promising properties towards the development of an oral delivery system for insulin.     

Optimizing dyes for dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) have emerged as an important cheap photovoltaic technology. Charge separation is initiated at the dye, bound at the interface of an inorganic semiconductor and a hole-transport material. Careful design of the dye can minimize loss mechanisms and improve light harvesting. Mass application of DSSCs is currently limited by manufacturing complexity and long-term stability associated with the liquid redox electrolyte used in the most-efficient cells. In this Minireview, dye design is discussed in the context of novel alternatives to the standard liquid electrolyte. Rapid progress is being made in improving the efficiencies of such solid and quasi-solid DSSCs which promises cheap, efficient, and robust photovoltaic systems.