Archive for the ‘Hot Article’ Category

Structural effects on the pH-dependent fluorescence of naphthalenic derivatives and consequences for sensing/switching

Graphical abstract: Structural effects on the pH-dependent fluorescence of naphthalenic derivatives and consequences for sensing/switchingNaphthalenic compunds have many applications in the fluorescent sensing/switching/logic systems.  In this paper from A. Prasanna de Silva and colleagues at Queen’s University in Belfast, the team examine a naphthalenic compund which is a fluorescent photoinduced electron transfer system of the ‘fluorophore-spacer-receptor’ format, whose fluorescence responds sharply to H+. Several structural variations of this compund are examined and it is deomonstrated that the naphthalenic derivatives display a range of H+-induced fluorescence switching actions.

For all the details read the article in full for free until 31st July:

Structural effects on the pH-dependent fluorescence of naphthalenic derivatives and consequences for sensing/switching
Shuai Zheng, P. L. Mark Lynch, Terence E. Rice, Thomas S. Moody, H. Q. Nimal Gunaratne and A. Prasanna de Silva
Photochem. Photobiol. Sci., 2012, Advance Article, DOI: 10.1039/C2PP25069A

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Photocatalytic Virus Inactivation by Titanium Dioxide

C2PP05414K The photocatalytic inactivation of influenza virus using titanium dioxide thin film is demonstrated in a recently published paper from Ryuichi Nakano and co-workers from Japan.  Titanium dioxide (TiO2) under ultraviolet (UV) light produces a strong oxidative effect and may therefore be used as a photocatalytic disinfectant.  Photocatalytic inactivation of bacteria is well known, however few studies have addressed virus inactivation. 

In this paper the inactivation of influenza virus is demonstrated using TiO2 nanoparticles immobilized on a glass plate.  Viral titers were dramatically reduced by the photocatalytic reaction and the influence of UV intensity, irradiation time and bovine serum albumin concentration in viral suspensions was investigated.  It was demonstrated that effective inactivation occurs under an environmental level of UV-A intensity.  In addition, the International Organization for Standardization (ISO) methodology for anti-bacterial effects of TiO2 photocatalysis can be useful for the evaluation of antiviral activity with only a small modification to the methodology.

Interested in knowing more?  Read the full article for free until June 14th by clicking the link below!

Photocatalytic inactivation of influenza virus by titanium dioxide thin film
Ryuichi Nakano, Hitoshi Ishiguro, Yanyan Yao, Jitsuo Kajioka, Akira Fujishima, Kayano Sunada, Masafumi Minoshima, Kazuhito Hashimoto and Yoshinobu Kubota
Photochem. Photobiol. Sci., 2012, DOI: 10.1039/C2PP05414K

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TT-dimer formation in DNA hairpins possessing TTT triads: effect of flanking purines

C2PP25089FIn this communication recently published online as an ‘Accepted Manuscript’ Frederick Lewis and co-workers from the USA and India investigate the effect of flanking purine bases on the 3’ vs the 5’-TT dimer upon UV irradiation of DNA hairpins possessing TTT steps with flanking purine bases. 

The study demonstrates moderate to high facial selectivity for the 3’-dimer over the 5’ dimer depending on the identity and location of flanking purine bases.  The effects of flanking purines on facial selectivity are attributed to a combination of their ground state conformational effects and electron transfer quenching.

Interested in knowing more? Read the full article for free until June 13th.

Facially-Selective Thymine-Thymine Photodimerization in TTT Triads
Prakash P Neelakandan, Zhengzheng Pan, Mahesh Hariharan and Frederick D Lewis
Photochem. Photobiol. Sci., 2012, Accepted Manuscript, DOI: 10.1039/C2PP25089F

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PPS Issue 5 now now online

Issue 5 coverPPS Issue 5 is now online and features bioluminescent mushrooms on the cover.  This image highlights the article from Cassius Stevani and co-workers from Brazil and the USA which provides evidence that a single bioluminescent system is shared by all known bioluminescent fungal lineages.  Click here to read the full issue.

Bioluminescence has evolved independently at least 40 times in different lineages of organisms.  Although all luminous systems involve the catalytic oxidation of a substrate (a luciferin) by a respective enzyme (a luciferase) or photoprotein the luciferases are not all homologous and each luminescence system has a luciferin with a specific structure.  Therefore each system is commonly only found within a single lineage. 

Although fungal bioluminescence is a common phenomenon, from the huge diversity in the Kingdom Fungi only 71 species have been verified as bioluminescent and they belong to four distantly related lineages.  There has, for a long time been uncertainty about the participation of a luciferase in fungal bioluminescence and only recently did this group prove its involvement confirming the enzymatic nature of bioluminescence (Photochem. Photobiol. Sci., 2009, 8, 1416)

The question that this study addresses is whether the mechanism of bioluminescence is the same in all four evolutionary lineages, or whether each lineage has a unique mechanism for light emission implying independent origins. Cross-reactions in all possible combinations of hot (substrate/luciferin) and cold (enzyme/luciferase) water extracts from species representing each of the four bioluminescent lineages resulted in light emission. In comparison, cross-reactions of these extracts with extracts from closely related non-luminescent species yielded no light emission.  These results suggest that all lineages share a single luminescent pathway and that this arose early in the evolution of the mushroom-forming order Agaricales.

Read the full article by clicking on the link below.  Free to read for 6 weeks!

Evidence that a single bioluminescent system is shared by all known bioluminescent fungal lineages
Anderson G. Oliveira, Dennis E. Desjardin, Brian A. Perry and Cassius V. Stevani
Photochem. Photobiol. Sci., 2012, 11, 848-852 DOI: 10.1039/C2PP25032B

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Semisynthetic zinc chlorins as chlorosomal mimics

C2PP25016KSemisynthetic zinc chlorins are shown for the first time to self-assemble in the absence of an intrinsic hydroxy group, which is always present in the chlorosomal bacteriochlorophylls (BChl’s) c, d and e.

Chlorosomes of green photosynthetic bacteria are the most efficient natural light-harvesting complexes.  Structural investigations have revealed fascinating self-assembled supramolecular chromophore architectures which are not scaffolded by protein matrices.  In this study, Teodor Silviu Balaban and co-workers from Germany, Japan and France have investigated the self-assembling ability of synthetic chlorins which lack the hydroxyl group but have at least two carbonyl groups.

The findings in this study may shed more light onto the forces and interactions governing the self-assembly of natural and modified BChl’s, and opens up possibilities for artificial light-harvesting systems mimicking the chlorosomal BChl’s in a truly biomimetic approach.

Read the article for free until 21st May by clicking the link below:

Water coordinated zinc dioxo-chlorin and porphyrin self-assemblies as chlorosomal mimics: variability of supramolecular interactions
Aldo Jesorka , Alfred R. Holzwarth, Andreas Eichhöfer, Chilla Malla Reddy , Yusuke Kinoshita, Hitoshi Tamiaki, Martin Katterle , Jean-Valère Naubron and Teodor Silviu Balaban
Photochem. Photobiol. Sci., 2012, Advance Article, DOI: 10.1039/C2PP25016K

This article is published as part of a themed issue in honour of Professor Kurt Schaffner on the occasion of his 80th birthday; look out for the issue in a few months!

You can keep up to date with the latest developments from PPS by signing up for free table of contents alerts.

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Energy transfer from a rhodamine antenna to a ruthenium–bipyridine center

Graphical abstract: Energy transfer from a rhodamine antenna to a ruthenium–bipyridine centerIn a recently published PPS article a team from Argentina demonstrate a way to enable a photodissociation reaction at longer wavelengths by utilising a modified rhodamine B (Rhod) cooridinated to a bis-bipyridine ruthenium (II) (Ru-bpy) phototrigger complex which has enhanced absorption of green light. 

Due to the fundamental photochemistry of the system it has not been possible to obtain a phototrigger presenting both high absorption at longer wavelengths (500nm) and a high photorelease quantum yield.  In this study the problem is circumvented by a coordinated fluorescent fragment harvesting long wavelength light and transferring this energy to the ruthenium centre, allowing high photoactivity at long wavelengths with very high absorptivity and high energy transfer quantum yield.

The behaviour of phototriggers, which releace a monodentate ligand through the d-d decomposition path, can be used to design caged compounds. Many molecules, including neurotransmitters and other biomolecules can be photodelivered using these complexes, which makes this one of the most promising techniques to cage drugs for photodynamic therapies, for neuroscience and for photoregulation of biological processes in general. This new mechanism found in a rhodamine-enhanced ruthenium phototrigger opens a full set of possibilities for designing Ru–bpy sensitizers, based in rhodamine and possibly other fluorescent dyes.

Read the full article for free until 10th April by clicking on the title below:

Energy transfer from a rhodamine antenna to a ruthenium–bipyridine center
Oscar Filevich, Beatriz García-Acosta and Roberto Etchenique
Photochem. Photobiol. Sci., 2012, Advance Article, DOI: 10.1039/C2PP05415A

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Dispersing oil spills with UV light and plant-based surfactants

Graphical abstract: Effects of visible and UV light on the characteristics and properties of crude oil-in-water (O/W) emulsionsWhat if you could disperse oil spills in the sea, such as the BP spill in the Gulf of Mexico, with air, sunlight, and an environmentally friendly botanical product?  These are the ingredients used in a recently published article from Professor Steven Suib and his team from the University of Conneticut, USA.  The study found that by adding a plant-based surfactant to a sample of synthetic seawater mixed with crude oil, pumping in air, stirring the sample and exposing it to ultraviolet light, the oil/water mixture quickly broke down into small particles.

The effects of visible and UV light on the characteristics and properties of Prudhoe Bay (PB) and South Louisiana (SL) emulsions were investigated to better understand the role of sunlight on the fate of spilled crude oils that form emulsions with a dispersant in the aquatic environment. The unique changes in physico-chemical properties of these emulsions as a result of photodegradation were investigated.

“Photodegradation of crude oil components can be an effective process for mitigating some of the damaging impacts resulting from oil spills in the aquatic environment,” the authors write. With the availability of modern, efficient UV-visible light sources, the process “may enable economic application of photodetoxification on a large-scale basis,” they say.

Interested in knowing more?  Read the article for free until March 20th.

Effects of visible and UV light on the characteristics and properties of crude oil-in-water (O/W) emulsions
Homer C. Genuino, Dayton T. Horvath, Cecil K. King’ondu, George E. Hoag, John B. Collins and Steven L. Suib
Photochem. Photobiol. Sci., 2012, Advance Article, DOI: 10.1039/C2PP05275J

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Multi-domain GFP-related proteins reported with a structure never seen before in nature

The 2008 Nobel prize was awarded for the discovery and development of the green fluorescent protein (GFP).  Since these initial discoveries almost 200 GFP-like Fluorescent proteins (FPs) have been described.  FPs have become indispensable in biomedical and basic research as a genetically encoded fluorescent label due to the unique ability of the protein family to synthesize light-emitting chromophores autocatalytically from their own three amino acid residues situated near the center of the FP globule.

Graphical abstract: Multi-domain GFP-like proteins from two species of marine hydrozoansA team from Austin, Texas have reported two new proteins displaying primary structures never before encountered in natural FPs in a recently published PPS article.  The proteins consist of multiple GFP-like domains repeated within the same polypeptide chain.  A two-domain green FP (abeGFP) and a four-domain orange-fluorescent FP (Ember) were isolated from the siphonophore Abylopsis eschscholtzii and an unidentified juvenile jellyfish (order Anthoathecata), respectively. 

There has never been any wild-type GFP-related proteins found which contain multiple GFP-like domains within a single polypeptide chain.  This paper describes two such proteins and explores possible relationships between individual domains within the four-domain orange-red protein from the anthoathecate jellyfish. 

The results reveal a previously unrecognized direction in which natural FPs have diversified, suggesting new avenues to look for FPs with novel and potentially useful features.

Interested in knowing more?  Read the full article for free until 15th February

Multi-domain GFP-like proteins from two species of marine hydrozoans
Marguerite E. Hunt, Chintan K. Modi, Galina V. Aglyamova, D. V. S. Ravikant, Eli Meyer and Mikhail V. Matz
Photochem. Photobiol. Sci., 2012, DOI: 10.1039/C1PP05238A

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Novel Hydrophilic Photolabile Protecting Groups for Hydroxyl Protection

Hydrophilic photolabile protecting groups (PPGs) for hydroxyl protection have been developed by Pengfei Wang and co-workers from the University of Alabama at Birmingham. 

PPGs are protecting groups that can be removed with photo irradiation, they very useful tools in a range of basic and applied research areas.  One of these applications is their use as ‘photocages’ where the photochemical removal of the photogages often takes place in aqueous environments meaning that solubility issues are central to the use of caged biomolecules.

hydrophilic PPGs

This team have previously developed a novel PPG for hydroxyl groups, 3-(dimethylamino)trityl (DMATr) but its hydrophobicity obstructs its wide applications in aqueous environments so in their recently published PPS article they report their efforts to improve its water solubility.  The new PPGs the team developed were derived from DMATr by replacing the two methyl groups with two hydrophilic butyryl groups. The new PPG reagents can be readily prepared and installed. They are stable in the dark but can be removed cleanly and efficiently in aqueous environments upon irradiation with a UV lamp or sunlight.

This paper is part of a themed issue on photoremovable protecting groups due to be published in 2012.

Interested in knowing more? Read the full article for free until 20th December 2011

Development of hydrophilic photolabile hydroxyl protecting groups
Haishen Yang, Lei Zhou and Pengfei Wang
Photochem. Photobiol. Sci.
, 2012, DOI: 10.1039/C1PP05281K

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New Porphyrin Shows Promise in Prevention of Malaria

Anopeles larvae The effects a new photoactivatable cationic prophyrin on components of freshwater ecosystems polluted by pathogenic agents responsible for malaria is investigated in a recent article from teams based at the University of Padova and the university of Camerino in Italy and Institut de Recherche en Science de la Santé in Burkina Faso. This paper is part of a research project which is aimed at the prevention of water- and vector-borne diseases such as Anopheles and Aedes larvae through adequate control of porphyrin-photosensitised processes.  These larvae are responsible for the worldwide diffusion of serious diseases, such as malaria and Dengue fever. 

Porphyrins are characterized by a macrocyclic molecule which absorbs visible light and transfers some of this absorbed energy to molecular oxygen forming reactive oxygen species (ROS).  Porphyrins and visible light are, individually, devoid of any bio-toxicity but when ROS are formed in a cell they are cytotoxic and cause irreversible cell death.  Their toxicity is the result of a multi-target mechanism involving parallel damage of a large number of cell constituents thus allowing very little opportunity for the selection of photoresistant microbial strains or the onset of mutagenic processes.  These photo processes show a high selectivity in space and time and are especially suitable to address problems connected with environmental pollution caused by the presence of large populations of potentially pathogenic microorganisms.

In collaboration with the company Frontier Scientific (Logan, Utah) the team from Italy and Burkina Faso have developed a specific porphyrin, named AquaFrin.  Studies by the teams in Italy demonstrated that AquaFrin, once mixed with standard larval food, is rapidly ingested by Anopheles and Aedes larvae and localises in their alimentary canal.  This makes the larvae photosensitive and the exposure of the porphyrin-loaded larvae to low intensity visible light induces an efficient death.  The successful extension of the technique to breeding sites of Anopheles larvae under natural conditions depends on the fulfilment of specific requirements:

  • Palatability of the porphyrin by the larvae when the photosensitising agent is introduced into their natural habitats was achieved by association of AquaFrin with selected carriers: both pollen and croquettes from cat food were successfully loaded and favourably competed with the natural larval food.
  • Prolonged Floatability of the carrier-porphyrin system in an aqueous milieu is essential since larvae preferentially feed at the water surface: this was achieved due to the presence of sufficiently large amounts of the highly hydrophilic AquaFrin.
  • Selectivity of the porphyrin photosensitising action toward larvae to minimize the risk of generalized damage to non-target constituents of the larval ecosystem.  Toward this aim, the size of the added porphyrin carrier particles is similar to the diameter of the esophagus of Anopheles larvae which facilitates their rapid ingestion, while the complex displays a long-term stability in water which avoids release of AquaFrin to the surrounding environment.

New Porphyrin Shows Promise in Prevention of MalariaIt is this final issue that the recently published PPS article concerns.  The article investigates the effects of the porphyrin on ciliated protozoa and branchiopod crustaceans which are components of the freshwater ecosystems that Anopheles larvae pollute.  These organisms are sensitive to the porphyrin but killing doses are an order of magnitude larger than those which are phototoxic to larvae.

Field studies have been performed in Burkina Faso and have given very positive results.  Pollen – or cat food-bound AquaFrin were added to endemic breeding sites of Anopeles larvae and when illuminated by daylight an extensive mortality was observed to occur within a few hours.

At present, the investigations are being extended to a number of areas in sub – Saharan countries, in order to validate and possibly refine the larvicidal protocol tailoring it to situations characterized by different species of Anopheles larvae, as well as different physical and chemical or optical quality of water, climatic conditions, biological composition of the ecosystem.

Interested in knowing more?  Read the full article for free until December 7th.

Effects of a new photoactivatable cationic porphyrin on ciliated protozoa and branchiopod crustaceans, potential components of freshwater ecosystems polluted by pathogenic agents and their vectors
Clara Fabris, Marina Soncin, Giulio Jori, Annette Habluetzel, Leonardo Lucantoni, Simon Sawadogo, Laura Guidolin and Olimpia Coppellotti
Photochem. Photobiol. Sci., 2012, DOI: 10.1039/C1PP05154G

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