1992 Merck–Frosst Award Lecture Orbital symmetry and the photochemistry of cyclobutene

1993 ◽  
Vol 71 (2) ◽  
pp. 147-155 ◽  
Author(s):  
William J. Leigh
Keyword(s):  
Ring Opening ◽  
Rydberg State ◽  
Uv Light ◽  
Light Sources ◽  
Unusual Behavior ◽  
Orbital Symmetry ◽  
Direct Photolysis ◽  
High Degree ◽  
Π State ◽  
Theoretical Results

Direct photolysis of alkyl-substituted cyclobutene derivatives in solution with monochromatic far-UV light sources results in competing ring opening to the corresponding substituted 1,3-butadiene derivatives and fragmentation to the corresponding alkene and alkyne via formal [2 + 2] cycloreversion. The excited states leading to the two types of products have been identified. Cycloreversion occurs stereospecifically and arises as a result of excitation of the π,R(3s) Rydberg state, which is of comparable energy to the π,π* state in alkylcyclobutenes. In spite of its stereospecificity, the reaction is nonconcerted; evidence is presented to suggest that it occurs by a mechanism involving [1,2] migration (ring contraction) to yield a cyclopropylcarbene intermediate, which then fragments to yield the alkyne and alkene. The stereochemistry at C3 and C4 in the starting cyclobutene is retained in the alkene produced in the reaction. Ring opening proceeds nonstereoselectively (from the π,π* singlet state) in well over a dozen systems that have been investigated, and possible mechanisms to account for this are discussed. It is proposed that orbital symmetry plays a role in the reaction, but only in the early stages of ring opening. Bicyclic cyclobutene derivatives in which the cyclobutene double bond is located across the [0] bridge undergo ring opening with a high degree of disrotatory stereoselectivity. Possible reasons for this unusual behavior are discussed in light of recent ab initio theoretical results.

scholarly journals Mono- and bithiophene-substituted diarylethene photoswitches with emissive open or closed forms

2019 ◽  
Vol 15 ◽  
pp. 2344-2354 ◽  
Author(s):  
A Lennart Schleper ◽  
Mariano L Bossi ◽  
Vladimir N Belov ◽  
Stefan W Hell
Keyword(s):  
Visible Light ◽  
Single Molecule ◽  
Ring Opening ◽  
Uv Light ◽  
Visible Region ◽  
Super Resolution ◽  
Ring Closure ◽  
Low Emission ◽  
Fluorescence Modulation ◽  
High Degree

We present a new series of photochromic 1,2-bis(2-ethylbenzo[b]thiophen-3-yl)perfluorocyclopentenes with an oxidized benzothiophene core (O) or a nonoxidized one, decorated with mono- (Th1) and bithiophene (Th2) units attached to positions 6 and 6′ (Sy = symmetric) or only to position 6 (As = asymmetric). “Oxidized” compounds have highly fluorescent closed forms emitting in the visible region (yellow to red). The dyes with nonoxidized benzothiophenes possess fluorescent open forms with rather low emission efficiency. The photoswitching kinetics was studied at several wavelengths with UV and visible light. New diarylethenes underwent ring-closure reactions by irradiation with UV light (365 nm, 405 nm), and the reversible ring-opening by irradiation with visible light (470 nm, 530 nm). The on-switching of fluorescence due to the ring-closure reaction was observed also with visible light of 470 nm (to an extent of 10% for compound SyOTh 1 ) and attributed to the Urbach tail effect. Due to a high degree of fluorescence modulation (>270), good fatigue resistance and large fluorescence quantum yield, compound SyOTh 1 emerged as a candidate for single-molecule based super-resolution fluorescence microscopy.

Cyclobutene photochemistry. Adiabatic photochemical ring opening of alkylcyclobutenes

1996 ◽  
Vol 74 (6) ◽  
pp. 951-964 ◽  
Author(s):  
William J. Leigh ◽  
J. Alberto Postigo ◽  
K.C. Zheng
Keyword(s):  
Ring Opening ◽  
Quantum Yields ◽  
Light Sources ◽  
Trans Isomers ◽  
Excited Singlet ◽  
Orbital Symmetry ◽  
Cis And Trans Isomers ◽  
Product Distributions ◽  
Reaction Proceeds ◽  
Cis And Trans

The photochemistry of the cis and trans isomers of a series of dimethylbicyclo[n 2.0]alk-(n + 2)-enes (n = 2–5) (bicyclic cyclobutene derivatives in which the C=C bond is shared by the two rings) in pentane solution is described. Irradiation of these compounds using monochromatic 193- or214-nm light sources results in ring opening to yield the corresponding 1,2-bis(1-ethylidene)cycloalkanes (C4–C7) in high chemical and quantum yields. In all cases, the reaction proceeds with a high (70–90%) degree of disrotatory stereoselectivity. Quantum yields for direct cis,trans photoisomerization of the isomeric E,E-and E,Z-1,2-bis(1-ethylidene)cycloalkanes have also been determined. The product distributions from irradiation of the cyclobutenes are wavelength dependent, but for 214-nm excitation the isomeric diene distributions obtained from cyclobutene ring opening agree fairly closely with those calculated from the quantum yields for cis,trans photoisomerization of the isomeric dienes on the assumption that the process involves purely disrotatory ring opening to yield a single diene isomer in the lowest excited singlet state. The results are consistent with an orbital-symmetry-controlled, adiabatic mechanism for ring opening. Key words: photochemistry, cyclobutene, electrocyclic, adiabatic, conical intersection, orbital symmetry.

The solution-phase photochemistry of 2-trifluoromethylnorbornene

1990 ◽  
Vol 68 (11) ◽  
pp. 1961-1966 ◽  
Author(s):  
N. Nguyen ◽  
B. E. Harris ◽  
K. B. Clark ◽  
W. J. Leigh
Keyword(s):  
Rydberg State ◽  
Singlet State ◽  
High Energy ◽  
Sigmatropic Rearrangement ◽  
Solution Phase ◽  
Excited Singlet ◽  
Direct Photolysis ◽  
Additional Support ◽  
193 Nm ◽  
Π State

The photochemistry of 2-trifluoromethylnorbornene in pentane solution has been investigated. Direct photolysis with 193 nm light yields 1-trifluoromethyl-2-norcarene in 90% yield, due to formal [1,3]-sigmatropic rearrangement, in addition to three other minor products. Chlorobenzene-sensitized photolysis affords photoreduction products, principally exo- and endo-2-trifluoromethylnorbornane and decane isomers, in addition to several products of higher molecular weight. On the basis of comparisons of the photochemistry of this compound to that previously reported for norbornene and 2-cyanonorbornene, as well as spectroscopic evidence, it is suggested that the lowest excited singlet state (the photoreactive state in solution) in 2-trifluoromethylnorbornene is the π, π* state. The results indicate that trifluoromethyl substitution has the effect of significantly raising the energy of the π,R(3s) Rydberg state in simple alkenes, without altering the high energy (ca. 6.5 eV) or the localized character of the alkene π, π* state. Furthermore, they lend additional support to the view that the carbene-derived products typically formed upon photolysis of alkenes in solution are derived from π,R(3s) excitation. Keywords: Rydberg, photolysis, far-uv, alkene, solution phase, singlet, triplet.

Cyclobutene photochemistry. Substituent and wavelength effects on the photochemical ring opening of monocyclic alkylcyclobutenes

1990 ◽  
Vol 68 (11) ◽  
pp. 1988-1997 ◽  
Author(s):  
William J. Leigh ◽  
Kangcheng Zheng ◽  
K. Brady Clark
Keyword(s):  
Ring Opening ◽  
Energy State ◽  
Wavelength Dependence ◽  
Uv Spectra ◽  
Solution Phase ◽  
Light Sources ◽  
Orbital Symmetry ◽  
Cis And Trans Isomers ◽  
193 Nm ◽  
Cis And Trans

The photochemical ring opening of cis- and trans-3,4-dimethyl-, 1,3,4-trimethyl-, and 1,2,3,4-tetramethylcyclobutene (1, 3, and 4, respectively) has been investigated in hydrocarbon solution with 193 nm and 214 nm light sources. Ring opening is non-stereospecific in all cases at both wavelengths. The ratio of dienes formed by the formally allowed to formally forbidden pathways in the photolysis of these compounds is highest (ca. 2) for the trimethylcyclobutenes, and approximately 1 for both cis and trans isomers of the di- and tetramethylcyclobutenes with 193 nm excitation. The diene distributions from photolysis of all compounds but cis-3 show slight wavelength dependence. Gas- and solution-phase UV absorption spectra are reported for 3 and 4, and indicate that there are at least three singlet excited states accessible in the 185–230 nm region in these molecules. The π,R(3s) state is the lowest energy state in the gas phase in 3 and 4. The results verify that orbital symmetry factors do not play a role (or a consistent one, at least) in controlling the stereochemistry of the reaction, but they do not allow a firm assignment of the excited state(s) responsible for ring opening. Direct photolysis of these compounds also results in fragmentation to yield Z-2-butene (from cis-3 and 4) or E-2-butene (from trans-3 and 4) in addition to propyne or 2-butyne. The 2-butenes are formed with greater than 90% stereospecificity in all cases. The structures of the four 3-methyl-2,4-hexadiene isomers obtained from photolysis of 3 have been assigned on the basis of 1H NMR spectroscopy and the results of thermolysis of the two cyclobutene isomers. Keywords: cyclobutene, photolysis, Rydberg, orbital symmetry, far-UV, solution phase, UV spectra.

Immobilization of ZnO Suspension on Glass Substrate to Remove Filtration During the Removal of Remazol Red R from Aqueous Solution

2016 ◽  
Vol 12 (6) ◽  
pp. 4127-4133
Author(s):  
Nazmul Kayes ◽  
Jalil Miah ◽  
Md. Obaidullah ◽  
Akter Hossain ◽  
Mufazzal Hossain
Keyword(s):  
Aqueous Solution ◽  
Glass Substrate ◽  
Uv Light ◽  
Aqueous Suspension ◽  
Light Irradiation ◽  
Zno Films ◽  
Light Sources ◽  
Zno Film ◽  
Semiconductor Oxides ◽  
Remazol Red

Photodegradation of textile dyes in the presence of an aqueous suspension of semiconductor oxides has been of growing interest. Although this method of destruction of dyes is efficient, the main obstacle of applying this technique in the industry is the time and cost involving separation of oxides from an aqueous suspension. In this research, an attempted was made to develop ZnO films on a glass substrate by simple immobilization method for the adsorption and photodegradation of a typical dye, Remazol Red R (RRR) from aqueous solution. Adsorption and photodegradation of  RRR were performed in the presence of glass supported ZnO film. Photodegradation of the dye was carried out by varying different parameters such as the catalyst dosage, initial concentrations of RRR, and light sources. The percentage of adsorption as well as photodegradation increased with the amount of ZnO, reaches a maximum and then decreased. Maximum degradation has been found under solar light irradiation as compared to UV-light irradiation. Removal efficiency was also found to be influenced by the pre-sonication of ZnO suspension.

scholarly journals Use of Electrosprayed Agave Fructans as Nanoencapsulating Hydrocolloids for Bioactives

Nanomaterials ◽  
2018 ◽  
Vol 8 (11) ◽  
pp. 868 ◽  
Author(s):  
Jorge Ramos-Hernández ◽  
Juan Ragazzo-Sánchez ◽  
Montserrat Calderón-Santoyo ◽  
Rosa Ortiz-Basurto ◽  
Cristina Prieto ◽  
...  
Keyword(s):  
Uv Light ◽  
Particle Morphology ◽  
Bioactive Compound ◽  
Processing Parameters ◽  
Degree Of Polymerization ◽  
Spherical Particles ◽  
Sem Images ◽  
High Degree ◽  
Thermal Stability Of ◽  
Β Carotene

High degree of polymerization Agave fructans (HDPAF) are presented as a novel encapsulating material. Electrospraying coating (EC) was selected as the encapsulation technique and β-carotene as the model bioactive compound. For direct electrospraying, two encapsulation methodologies (solution and emulsion) were proposed to find the formulation which provided a suitable particle morphology and an adequate concentration of β-carotene encapsulated in the particles to provide a protective effect of β-carotene by the nanocapsules. Scanning electron microscopy (SEM) images showed spherical particles with sizes ranging from 440 nm to 880 nm depending on the concentration of HDPAF and processing parameters. FTIR analysis confirmed the interaction and encapsulation of β-carotene with HDPAF. The thermal stability of β-carotene encapsulated in HDPAF was evidenced by thermogravimetric analysis (TGA). The study showed that β-carotene encapsulated in HDPAF by the EC method remained stable for up to 50 h of exposure to ultraviolet (UV) light. Therefore, HDPAF is a viable option to formulate nanocapsules as a new encapsulating material. In addition, EC allowed for increases in the ratio of β-carotene:polymer, as well as its photostability.

scholarly journals Beeporter: a high-throughput tool for non-invasive analysis of honey bee virus infection

2021 ◽  
Author(s):  
Jay D. Evans ◽  
Olubukola Banmeke ◽  
Evan C. Palmer-Young ◽  
Yanping Chen ◽  
Eugene V. Ryabov
Keyword(s):  
Virus Infection ◽  
Honey Bee ◽  
High Throughput ◽  
Honey Bees ◽  
High Throughput Screening ◽  
Fluorescent Protein ◽  
Imaging System ◽  
Uv Light ◽  
Light Sources ◽  
Deformed Wing Virus

ABSTRACTHoney bees face numerous pests and pathogens but arguably none are as devastating as Deformed wing virus (DWV). Development of antiviral therapeutics and virus-resistant honey bee lines to control DWV in honey bees is slowed by the lack of a cost-effective high-throughput screening of DWV infection. Currently, analysis of virus infection and screening for antiviral treatments in bees and their colonies is tedious, requiring a well-equipped molecular biology laboratory and the use of hazardous chemicals. Here we utilize a cDNA clone of DWV tagged with green fluorescent protein (GFP) to develop the Beeporter assay, a method for detection and quantification of DWV infection in live honey bees. The assay involves infection of honey bee pupae by injecting a standardized DWV-GFP inoculum, followed by incubation for up to 44 hours. GFP fluorescence is recorded at intervals via commonly available long-wave UV light sources and a smartphone camera or a standard ultraviolet transilluminator gel imaging system. Nonlethal DWV monitoring allows high-throughput screening of antiviral candidates and a direct breeding tool for identifying honey bee parents with increased antivirus resistance. For even more rapid drug screening, we also describe a method for screening bees using 96-well trays and a spectrophotometer.

scholarly journals Visible-Light Photoswitching of G-Quadruplex Ligand Binding Mode Allows Reversible Control of G-Tetrad Structure

2020 ◽  
Author(s):  
Michael O'Hagan ◽  
Javier Ramos Soriano ◽  
Susanta Haldar ◽  
Juan Carlos Morales ◽  
Adrian Mulholland ◽  
...  
Keyword(s):  
Ligand Binding ◽  
Visible Light ◽  
Uv Light ◽  
Binding Mode ◽  
High Energy ◽  
Light Sources ◽  
Biologically Relevant ◽  
G Quadruplex ◽  
Potential Applications ◽  
Robust Regulation

<div><p>Photoresponsive ligands for G-quadruplex oligonucleotides (G4) offer exciting opportunities for the reversible regulation of these assemblies with potential applications in biological chemistry and responsive nanotechnology. However, achieving the robust regulation of G4 ligand activity with low-energy visible light sources that are easily accessible and compatible with biological systems remains a significant challenge to realizing these applications. Herein, we report the G4-binding properties of a photoresponsive dithienylethene (DTE). We demonstrate the first example of G4-specific acceleration of the photoswitching kinetics of a small molecule and the visible-light mediated switching of the G4 ligand binding mode in physiologically-relevant conditions, which in turn allows control over the G4 tetrad structure of telomeric G4 in potassium buffer. The process is fully reversible and avoids the need for high-energy UV light. This affords an efficient, practical and biologically-relevant means of control that may be applied in the generation of new responsive G4/ligand supramolecular systems.</p></div><br>

scholarly journals Researching CdZnS/ZnS (GT) Quantum Dots in Cathodoluminescent Mode

2019 ◽  
Vol 8 (9S2) ◽  
pp. 841-843
Keyword(s):  
Quantum Dots ◽  
Research And Development ◽  
Uv Light ◽  
Spectral Characteristics ◽  
Light Sources ◽  
Application Field ◽  
Medium Pressure

Application field of UV light sources is getting larger at the last decades. Among the most widespread are high and medium pressure vacuum lamps. But there currently is a trend of moving away from using mercury both in household applications and manufacturing. This creates a necessity to conduct research and development for UV sources made and operating without Hg. Cathodoluminescent UV sources are in this category. One of the possible ways to create a viable UV anode phosphor is using quantum dots with needed spectral characteristics.

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