Site-specific bioconjugation and nuclear imaging.

Monoclonal antibodies and antibody fragments have proven to be highly effective vectors for the delivery of radionuclides to target tissues for positron emission tomography (PET) and single-photon emission computed tomography (SPECT). However, the stochastic methods that have traditionally been used to attach radioisotopes to these biomolecules inevitably produce poorly defined and heterogeneous probes and can impair the ability of the immunoglobulins to bind their molecular targets. In response to this challenge, an array of innovative site-specific and site-selective bioconjugation strategies have been developed, and these approaches have repeatedly been shown to yield better-defined and more homogeneous radioimmunoconjugates with superior in vivo performance than their randomly modified progenitors. In this Current Opinion in Chemical Biology review, we will examine recent advances in this field, including the development - and, in some cases, clinical translation - of nuclear imaging agents radiolabeled using strategies that target the heavy chain glycans, peptide tags, and unnatural amino acids.

Modular Enzyme- and Light-Based Activation of Cyclopropene-Tetrazine Ligation.

We describe a modular activation strategy for cyclopropene-tetrazine ligation. This activation strategy uses chemically diverse enzyme- or photolabile protecting groups as cyclopropene reactivity cages. The linkages between the caging groups and cyclopropene are through carbamates, thus permitting the application of diverse cages to allow bioorthogonal reactivity by administering enzymes or light.

Organic Photosensitizers Incorporating Rigidified Dithieno[3,2-f:2',3'-h]quinoxaline Segment Tethered with Thiophene Substitutes for Dye-Sensitized Solar Cells.

Metal-free D-π-RS-π-A type sensitizers, consisting of triphenylamine as the electron donor, 2,3-bis(3-(2-ethylhexyl)-5-methylthiophen-2-yl)dithieno[3,2-f:2',3'-h]quinoxaline (DTQT) as the rigidified conjugation spacer (RS), thiophene as the π-spacer, and 2-cyanoacrylic acid as the acceptor/anchor, have broad absorption spectra ranging from 350 to 550 nm and a high molar extinction coefficient up to >46 200 M(-1) cm(-1). Under simulated AM 1.5 G illumination, the dye-sensitized solar cells (DSSCs) fabricated from the dyes exhibited light-to-electricity conversions in the range of 6.78% to 8.27%. The best efficiency is slightly higher than that of N719-based standard DSSC (7.92%). The efficiency can be further boosted to 8.51% by optimizing the concentration of LiI electrolyte.

Organic Dyes Incorporating the Dithieno[3,2-f:2',3'-h]quinoxaline Moiety for Dye-Sensitized Solar Cells.

New donor-acceptor'-acceptor-type sensitizers (QBT dyes), comprising arylamine as the electron donor, dithieno[3,2-f:2',3'-h]quinoxaline as the internal acceptor, and 2-cyanoacrylic acid as both the acceptor and anchor, have been synthesized. The QBT dyes have broad absorption spectra covering the range of λ=368-487 nm with a highest molar extinction coefficient of up to approximately 40 000 M(-1) cm(-1) . The light-to-electricity conversion efficiencies of the dye-sensitized solar cells (DSSCs) fabricated from the dyes range from 6.11 to 7.59 % under simulated AM 1.5 G illumination. Upon addition of a threefold concentration of chenodeoxycholic acid as the co-adsorbent, the best performance cell has a power-conversion efficiency of 8.41 %, which is higher than that of the N719-based standard DSSC (8.27 %).

Eugenic metal-free sensitizers with double anchors for high performance dye-sensitized solar cells.

A series of new phenothiazine-based dyes (HL5-HL7) with double acceptors/anchors have been synthesized and used as the sensitizers for highly efficient dye-sensitized solar cells (DSSCs). Among them, the HL7-based cell exhibits the best efficiency of 8.32% exceeding the N719-based cell (7.35%) by ∼13%.

Organic dyes incorporating the dithieno[3',2':3,4;2″,3″:5,6]benzo[1,2-c]furazan moiety for dye-sensitized solar cells.

New D-π-A'-π-A type sensitizers (JH dyes), comprised arylamine as the electron donor, dithieno[3',2':3,4;2″,3″:5,6]benzo[1,2-c]furazan (DTBF) in the conjugated spacer, and 2-cyanoacrylic acid as both the acceptor and anchor, have been synthesized. The JH dyes have broad absorption spectra covering the range of 350 to 600 nm with the highest molar extinction coefficient up to >40 000 M(-1) cm(-1). The dye-sensitized solar cells (DSSCs) fabricated from the dyes exhibited light-to-electricity conversions ranging from 1.42 to 6.18% under simulated AM 1.5 G illumination. Upon adding 10 mM CDCA as the coadsorbent, the best performance cell has the power conversion efficiency of 7.33%, which is close to that of N719-based standard DSSC (7.56%).

High-performance dye-sensitized solar cells based on phenothiazine dyes containing double anchors and thiophene spacers.

A series of new push-pull phenothiazine-based dyes (HL1-HL4) featuring various π spacers (thiophene, 3-hexylthiophene, 4-hexyl-2,2'-bithiophene) and double acceptors/anchors have been synthesized, characterized, and used as sensitizers for dye-sensitized solar cells (DSSCs). Among them, the best conversion efficiency (7.31%) reaches approximately 99% of the N719-based (7.38%) DSSCs fabricated and measured under similar conditions. The dyes with two anchors have more efficient interfacial charge generation and transport compared with their congeners with only single anchor. Incorporation of hexyl chains into the π-conjugated spacer of these double-anchoring dyes can efficiently suppress dye aggregation and reduce charge recombination.