Exact solution of the excited-state geminate A*+B <==> C*+D reaction with two different lifetimes and quenching

The authors obtain, in the Laplace transform space, the exact analytic solution for the Green function and survival probabilities for the excited-state diffusion-influenced reversible geminate reaction, A*+B <==> C*+D, with two different lifetimes and in the presence of an added quenching process. This extends a previous investigation by Popov and Agmon [J. Chem. Phys. 117, 5770 (2002)] of the ground-state reaction without quenching. The long-time asymptotic behavior of the survival probabilities is obtained in the time domain. It is found to be different from the equal-lifetime case. This paper also provides a useful short-time approximation for the kinetics.     

Preparation of nanoporous MgO-coated TiO2 nanoparticles and their application to the electrode of dye-sensitized solar cells

Sol-gel-derived Mg(OH)(2) gel was coated onto TiO(2) nanoparticles, and the subsequent thermal topotactic decomposition of the gel formed a highly nanoporous MgO crystalline coating. The specific surface area of the electrode that was prepared from the core-shell-structured TiO(2) nanoparticles significantly increased compared with that of the uncoated TiO(2) electrode. The increase in the specific surface area of the MgO-coated TiO(2) electrode was attributed to the highly nanoporous MgO coating layer that resulted from the topotactic reaction. Dye adsorption behavior and solar cell performance were significantly enhanced by employing the MgO-coated TiO(2) electrode. Optimized coating of a MgO layer on TiO(2) nanoparticles enhanced the energy conversion efficiency as much as 45% compared to that of the uncoated TiO(2) electrode. This indicates that controlling the extrinsic parameters such as the specific surface area is very important to improve the energy conversion efficiency of TiO(2)-based solar cells.     

Synthesis and properties of organosoluble poly(amide imide imide)s based on tetraimide dicarboxylic acid condensed from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline,and trimellitic anhydride and various aromatic diamines

A novel tetraimide dicarboxylic acid was synthesized with the ring‐opening addition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline, and trimellitic anhydride in a 1/2/2 molar ratio in N‐methyl‐2‐pyrrolidone followed by azeotropic condensation to tetraimide dicarboxylic acid. A series of poly(amide imide imide)s (PAIIs) with inherent viscosities of 0.8–1.1 dL/g were prepared from tetraimide dicarboxylic acid with various aromatic diamines by direct polycondensation. Most of the PAIIs were readily soluble in a variety of amide polar solvents and even in less polar m‐cresol and pyridine. Solvent‐cast films had tensile strengths ranging from 99 to 106 MPa, elongations at break ranging from 8 to 13%, and initial moduli ranging from 2.0 to 2.3 GPa. The glass‐transition temperatures of these PAIIs were recorded at 244–276 °C. They had 10% weight losses at temperatures above 520 °C in air or nitrogen atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1092–1102, 2002     

Anode Magnetron Enhanced DC Glow Discharge Processes for Plasma Surface Cleaning and Polymerization

The objective of this study was to examine some fundamental factors involved in the design and construction of the anode magnetron dc glow discharge processes as well as its performance in plasma cleaning and polymerization. Those advantages of anode magnetron include the capability of the magnetron to operate at low pressure, as well as decreasing the thickness of cathode dark space, i.e., the negative glow which contains a higher concentration of ions and active species was more closely to the cathode surface, which makes the plasma surface cleaning and polymerization an effective and uniform processes. The deposition rate at a given discharge power is increased by the presence of anode magnetrons, and is also much higher relative to rf and af. The refractive index of dc plasma film at a given polymer thickness (such as TMS, 70 nm, RI: 2.4) is higher than rf, af, and cascade arc plasma (RI: 1.6–1.7).     

Facile Synthesis and Palladium‐Catalyzed Cross‐Coupling Reactions of 2,3‐Bis(pinacolatoboryl)‐1,3‐butadiene

Treatment of 1,1‐bis(pinacolatoboryl)ethene with an excess of 1‐bromo‐1‐lithioethene gave 2,3‐bis(pinacolatoboryl)‐1,3‐butadiene in high yield. Palladium‐catalyzed cross‐coupling of the resulting diborylbutadiene with aryl iodides took place smoothly in the presence of a catalytic amount of Pd(OAc)₂/PPh₃ and aqueous KOH to give 2,3‐diaryl‐1,3‐butadienes in good yields. The coupling reaction with commercially available 4‐acetoxyphenylmethyl chloride under the same conditions followed by hydrolysis of the acetyl groups gave anolignan B in a one‐pot manner. A variety of [3]‐ to [6]dendralenes were synthesized by palladium‐catalyzed coupling of the diene or 1,1‐bis(pinacolato)borylethene with alkenyl or dienyl halides, respectively, in good yields.     

Photochemical valence tautomerization of berberinephenolbetaines to 8,14-cycloberbines,versatile aziridine derivatives for spirobenzylisoquinolines

Irradiation of the berberinephenolbetaines ($\text{8}$$\text{a}$, $\text{8}$$\text{b}$, and $\text{8}$$\text{c}$) effected valence tautomerization to give the 8,14-cycloberbines ($\text{9}$$\text{a}$, $\text{9}$$\text{b}$, and $\text{9}$$\text{c}$), the aziridine derivatives, in high yield. The 8,14-cycloberbines were efficiently converted to the spirobenzylisoquinolines by regioselective C bond cleavage.     

Machine-learning algorithms for asthma,COPD, and lung cancer risk assessment using circulating microbial extracellular vesicle data and their application to assess dietary effects

Although mounting evidence suggests that the microbiome has a tremendous influence on intractable disease, the relationship between circulating microbial extracellular vesicles (EVs) and respiratory disease remains unexplored. Here, we developed predictive diagnostic models for COPD, asthma, and lung cancer by applying machine learning to microbial EV metagenomes isolated from patient serum and coded by their accumulated taxonomic hierarchy. All models demonstrated high predictive strength with mean AUC values ranging from 0.93 to 0.99 with various important features at the genus and phylum levels. Application of the clinical models in mice showed that various foods reduced high-fat diet-associated asthma and lung cancer risk, while COPD was minimally affected. In conclusion, this study offers a novel methodology for respiratory disease prediction and highlights the utility of serum microbial EVs as data-rich features for noninvasive diagnosis.Subject terms: Respiratory tract diseases, Machine learning, Predictive markers     

An Fc variant with two mutations confers prolonged serum half-life and enhanced effector functions on IgG antibodies

The pH-selective interaction between the immunoglobulin G (IgG) fragment crystallizable region (Fc region) and the neonatal Fc receptor (FcRn) is critical for prolonging the circulating half-lives of IgG molecules through intracellular trafficking and recycling. By using directed evolution, we successfully identified Fc mutations that improve the pH-dependent binding of human FcRn and prolong the serum persistence of a model IgG antibody and an Fc-fusion protein. Strikingly, trastuzumab-PFc29 and aflibercept-PFc29, a model therapeutic IgG antibody and an Fc-fusion protein, respectively, when combined with our engineered Fc (Q311R/M428L), both exhibited significantly higher serum half-lives in human FcRn transgenic mice than their counterparts with wild-type Fc. Moreover, in a cynomolgus monkey model, trastuzumab-PFc29 displayed a superior pharmacokinetic profile to that of both trastuzumab-YTE and trastuzumab-LS, which contain the well-validated serum half-life extension Fcs YTE (M252Y/S254T/T256E) and LS (M428L/N434S), respectively. Furthermore, the introduction of two identified mutations of PFc29 (Q311R/M428L) into the model antibodies enhanced both complement-dependent cytotoxicity and antibody-dependent cell-mediated cytotoxicity activity, which are triggered by the association between IgG Fc and Fc binding ligands and are critical for clearing cancer cells. In addition, the effector functions could be turned off by combining the two mutations of PFc29 with effector function-silencing mutations, but the antibodies maintained their excellent pH-dependent human FcRn binding profile. We expect our Fc variants to be an excellent tool for enhancing the pharmacokinetic profiles and potencies of various therapeutic antibodies and Fc-fusion proteins.Subject terms: Antibody therapy, Molecularly targeted therapy, Drug development