Porpholactone Chemistry: An Emerging Approach to Bioinspired Photosensitizers with Tunable Near-Infrared Photophysical Properties.

08:00 EDT 12th July 2019 | BioPortfolio

Summary of "Porpholactone Chemistry: An Emerging Approach to Bioinspired Photosensitizers with Tunable Near-Infrared Photophysical Properties."

Chlorophylls, known as the key building blocks of natural light-harvesting antennae, are essential to utilize solar energy from visible to near-infrared (NIR) region during the photosynthesis process. The fundamental studies for the relationship between structure and photophysical properties of chlorophylls disclosed the importance of -peripheral modification and thus boosted the fast growth of NIR absorbing/emissive porphyrinoids via altering the extent of π-conjugation and the degree of distortion from the planarity of macrocycle. Despite the tremendous progress made in various porphyrin-based synthetic models, it still remains a challenge to precisely modulate photophysical properties through fine-tuning of -peripheral structures in the way natural chlorophylls do. With this in mind, we initiated a program and focused on -CF-substituted porpholactone (), in which one -pyrrolic double bond was replaced by a lactone moiety, as an attractive platform to construct the bioinspired library of NIR porphyrinoids. In this Account, we summarize our recent contributions to the bioinspired design, synthesis, photophysical characterization, and applications of porpholactones and their derivatives. We have developed a general, convenient method to directly prepare porpholactones in large scale up to gram, which forms the chemical basis of porpholactone chemistry. By modulation of the saturation level and in particular regioisomerization of -dilactone moieties, a synthetic library constituted by a series of porpholactones and their derivatives has been established. Thanks to the electron-withdrawing nature of lactone moiety, derivation of the saturation levels gives help to build stable models for chlorin, bacteriochlorin, and tunichlorin. It is worth noting that regioisomerization of dilactone moieties mimics the relative orientation of -substituents in natural chlorophylls and hemes, which was considered as the key factor to tune NIR absorption and reactivity. Porpholactones can illustrate the capability of fine-tuning photophysical properties including the excited triplet states by subtle alteration of -peripheral structures in the presence of transition metals and lanthanides (Ln). Furthermore, they can serve as efficient photosensitizers for singlet oxygen and NIR Ln, showing potential applications in cell imaging and photocytotoxicity studies. The high luminescence, tunable structures, high cellular uptake, and intense NIR absorption render them as promising and competitive candidates for theranostics and . Therefore, extending the studies of "porpholactone chemistry" not only tests the fundamental understanding of the structure-function relationship that governs NIR photophysical properties of natural tetrapyrrole cofactors such as chlorophylls but also provides the guiding principles for the bioinspired design of NIR luminescent molecular probes with various applications. Taken together, as a new synthetic porphyrin derivative, porpholactone chemistry shines light on synthetic porphyrin, bioinorganic, and lanthanide chemistry.


Journal Details

This article was published in the following journal.

Name: Accounts of chemical research
ISSN: 1520-4898


DeepDyve research library

PubMed Articles [15274 Associated PubMed Articles listed on BioPortfolio]

Boron Dipyrromethene Nano-Photosensitizers for Anticancer Phototherapies.

As traditional phototherapy agents, boron dipyrromethene (BODIPY) photosensitizers have attracted increasing attention due to their high molar extinction coefficients, high phototherapy efficacy, and ...

Bioinspired Functional Catechol Derivatives Through Simple Thiol Conjugate Addition.

The combination of the surface-adhesive properties of catechol rings and functional moieties conveying specific properties is very appealing to materials chemistry, but the preparation of catechol der...

Bioinspired poly(vinyl alcohol)/zeolite composite coating with multifunctional integration.

Underwater superoleophobic coatings have attracted significant research attention for their excellent oil-repellent properties. However, the major challenge for current coatings is poor performance un...

Porphyrinoid photosensitizers mediated photodynamic inactivation against bacteria.

The multi-drug resistant bacteria have become a serious problem complicating therapies to such a degree that often the term "post-antibiotic era" is applied to describe the situation. The infections w...

Atomically Precise Bimetallic Nanoclusters as Photosensitizers in Photoelectrochemical Cells.

An atomically precise bimetallic nanocluster, Au24Ag20-(PhCC)20(SPy)4Cl2 (1), is for the first time employed as photosensitizer for photoelectrochemical application. The sensitization of TiO2 nanotube...

Clinical Trials [2596 Associated Clinical Trials listed on BioPortfolio]

Clinical Implication of the Tunable Crack Sensor

[Development of diagnosis algorism for paroxysmal arrhythmia using ultra-thin resistive membrane: a pilot study] Comparison of blood pressure via tunable crack sensor and invasive pressure...

A Tunable-tension Transobturator Tape vs Standard Transobturator Midurethral Tape for Stress Urinary Incontinence

This is the prospective randomized parallel groups trial with two participating centers (Department of Urology, Saint Petersburg State University Clinic of advanced medical technologies n....

An Open Label Study to Assess the Effect of BLI800 on Safety and Clinical Chemistry Parameters

To evaluate and compare the effects on safety measures and clinical chemistry after BLI800 in two groups of patients and one group of healthy controls. The patient groups will be those wi...

Performance Evaluation of In-Vitro Diagnostic Device

This is an interim report for POC testing of skyla Clinical Chemistry Analyzer and four skyla Test Systems (ALB, BUN, GLU, and TP). The analyses are performed with skyla Clinical Chemistry...

Investigation of Endemic and Emerging Diseases in Populations of Homeless Households in Marseille.

Hypothesis: Homeless people have infections not diagnosed with a potential impact on their health status. Main Purpose: Improve the etiological diagnosis of endemic and/or emerging...

Medical and Biotech [MESH] Definitions

Organic chemistry methodology that mimics the modular nature of various biosynthetic processes. It uses highly reliable and selective reactions designed to "click" i.e., rapidly join small modular units together in high yield, without offensive byproducts. In combination with COMBINATORIAL CHEMISTRY TECHNIQUES, it is used for the synthesis of new compounds and combinatorial libraries.

Chemistry dealing with the composition and preparation of agents having PHARMACOLOGIC ACTIONS or diagnostic use.

Field of chemistry pertaining to the study of inorganic compounds or ions and their interactions with biological ligands at the molecular level.

The branch of chemistry dealing with detection (qualitative) and determination (quantitative) of substances. (Grant & Hackh's Chemical Dictionary, 5th ed)

A chemistry-based technology in which sets of reactions, for solution or solid-phase synthesis, are used to create molecular libraries for analysis of compounds on a large scale.

Quick Search


DeepDyve research library

Searches Linking to this Article