scholarly journals Similar chemical structures, dissimilar triplet quantum yields: a CASPT2 model rationalizing the trend of triplet quantum yields in nitroaromatic systems

2019 ◽  
Vol 21 (20) ◽  
pp. 10514-10522 ◽  
Author(s):  
Angelo Giussani ◽  
Graham A. Worth
Keyword(s):  
Quantum Yields ◽  
Chemical Structures ◽  
Similar Chemical ◽  
Triplet Quantum Yields

S1/S0 accessibility strongly influences the triplet quantum yields of nitronaphthalenes.

scholarly journals Synthesis and Biological Activity of New Brassinosteroid Analogs of Type 24-Nor-5β-Cholane and 23-Benzoate Function in the Side Chain

2021 ◽  
Vol 22 (9) ◽  
pp. 4808
Author(s):  
Nitza Soto ◽  
Karoll Ferrer ◽  
Katy Díaz ◽  
César González ◽  
Lautaro Taborga ◽  
...  
Keyword(s):  
Good Alternative ◽  
Positive Control ◽  
Starting Material ◽  
Chemical Structures ◽  
High Reaction ◽  
Similar Chemical ◽  
Synthetic Procedure ◽  
Hyodeoxycholic Acid ◽  
External Stresses

Brassinosteroids are polyhydroxysteroids that are involved in different plants’ biological functions, such as growth, development and resistance to biotic and external stresses. Because of its low abundance in plants, much effort has been dedicated to the synthesis and characterization of brassinosteroids analogs. Herein, we report the synthesis of brassinosteroid 24-nor-5β-cholane type analogs with 23-benzoate function and 22,23-benzoate groups. The synthesis was accomplished with high reaction yields in a four-step synthesis route and using hyodeoxycholic acid as starting material. All synthesized analogs were tested using the rice lamina inclination test to assess their growth-promoting activity and compare it with those obtained for brassinolide, which was used as a positive control. The results indicate that the diasteroisomeric mixture of monobenzoylated derivatives exhibit the highest activity at the lowest tested concentrations (1 × 10−8 and 1 × 10−7 M), being even more active than brassinolide. Therefore, a simple synthetic procedure with high reaction yields that use a very accessible starting material provides brassinosteroid synthetic analogs with promising effects on plant growth. This exploratory study suggests that brassinosteroid analogs with similar chemical structures could be a good alternative to natural brassinosteroids.

Molecular Motion Analysis of 5CB in PDLCs Using Solid-State 13C NMR Relaxation Spectroscopy

1993 ◽  
Vol 47 (7) ◽  
pp. 933-941 ◽  
Author(s):  
Karen L. Buchert ◽  
Jack L. Koenig ◽  
Shi-Qing Wang ◽  
John L. West
Keyword(s):  
Liquid Crystal ◽  
Solid State ◽  
Polymer Matrix ◽  
Nmr Relaxation ◽  
Domain Size ◽  
Chemical Structures ◽  
Similar Chemical ◽  
Polymer Dispersed ◽  
Submicron Droplets ◽  
Significant Change

In samples of polymer-dispersed liquid crystals (PDLCs), submicron droplets of liquid crystal reside within a polymer matrix. By the use of the cross polarization technique for solid-state 13C NMR spectroscopy, the NMR spectrum of the liquid crystal can be obtained without interference from the polymer spectrum, even though the two materials have some similar chemical structures. Both 13C T1 and 13C T1 ρ relaxation experiments were performed on a PDLC system of 5CB in epoxy as a function of 5CB domain size. The 13C T1 relaxation constants and the localized motions they measure showed no significant change over the liquid crystal domain size studied. However, the 13C T1 ρ relaxation constants and the segmental motions of molecules they measure revealed a significant change over the liquid crystal domain size studied. Therefore, the 13C T1 ρ values can be used to determine the change in mobility of the molecular segments of the SCB molecules resulting from increased interaction between the liquid crystal and the polymer matrix and to further understand the importance of the molecular motions of the liquid crystal in the switching phenomenon for PDLC materials.

scholarly journals Competitive cocrystallization and its application in the separation of flavonoids

IUCrJ ◽  
2021 ◽  
Vol 8 (2) ◽  
pp. 195-207
Author(s):  
Yanming Xia ◽  
Yuanfeng Wei ◽  
Hui Chen ◽  
Shuai Qian ◽  
Jianjun Zhang ◽  
...  
Keyword(s):  
Free Energy ◽  
Formation Constant ◽  
Energy Gap ◽  
Hirshfeld Surface ◽  
Methanol Solution ◽  
Model Compounds ◽  
Electronic Density ◽  
Chemical Structures ◽  
Similar Chemical ◽  
Interaction Contribution

Recently, cocrystallization has been widely employed to tailor physicochemical properties of drugs in the pharmaceutical field. In this study, cocrystallization was applied to separate natural compounds with similar structures. Three flavonoids [baicalein (BAI), quercetin (QUE) and myricetin (MYR)] were used as model compounds. The coformer caffeine (CAF) could form cocrystals with all three flavonoids, namely BAI–CAF (cocrystal 1), QUE–CAF (cocrystal 2) and MYR–CAF (cocrystal 3). After adding CAF to methanol solution containing MYR and QUE (or QUE and BAI), cocrystal 3 (or cocrystal 2) preferentially formed rather than cocrystal 2 (or cocrystal 1), indicating that flavonoid separation could be achieved by competitive cocrystallization. After co-mixing the slurry of two flavonoids with CAF followed by centrifugation, the resolution ratio that could be achieved was 70–80% with purity >90%. Among the three cocrystals, cocrystal 3 showed the lowest formation constant with a negative Gibbs free energy of nucleation and the highest energy gap. Hirshfeld surface analysis and density of states analysis found that cocrystal 3 had the highest strong interaction contribution and the closest electronic density, respectively, followed by cocrystal 2 and cocrystal 1, suggesting CAF could competitively form a cocrystal with MYR much more easily than QUE and BAI. Cocrystallization is a promising approach for green and effective separation of natural products with similar chemical structures.

scholarly journals Dinucleoside polyphosphates act as 5’-RNA caps in Escherichia coli

2019 ◽  
Author(s):  
Oldřich Hudeček ◽  
Roberto Benoni ◽  
Martin Culka ◽  
Martin Hubálek ◽  
Lubomír Rulíšek ◽  
...  
Keyword(s):  
Escherichia Coli ◽  
Rna Stability ◽  
E Coli ◽  
Chemical Structures ◽  
Additional Layer ◽  
Similar Chemical ◽  
Decapping Enzyme ◽  
Almost All ◽  
Dinucleoside Polyphosphates ◽  
Rna Caps

Dinucleoside polyphosphates (NpnNs), discovered more than 50 years ago,1 are pleiotropic molecules present in almost all types of cells.2 It has been shown that their intracellular concentration can under stress conditions increase from the µM to mM range 2,3. However, the cellular roles and mechanisms of action of NpnNs are still speculative4,5. They have never been considered as part of the RNA, even though they have similar chemical structures as already known RNA caps, such as the nicotinamide adenine dinucleotide (NAD)6-8 and 7-methylguanylate cap9. Here, we show that both methylated and non-methylated Npn Ns serve as RNA caps in Escherichia coli (E. coli). NpnNs are excellent substrates for T7 and E. coli RNA polymerases (RNAP) and efficiently initiate transcription. Further, we demonstrate that the E. coli decapping enzyme RNA 5’ pyrophosphohydrolase (RppH) is able to remove the NpnNs-cap from the RNA. RppH was, however, not able to cleave the methylated forms of the NpnN-caps, suggesting that the methylation adds an additional layer to the RNA stability regulation. Our work introduces an original perspective on the chemical structure of RNA in prokaryotes and the function of RNA caps. This is the first evidence that small molecules like NpnNs can act in cells via their incorporation into RNA and influence the cellular metabolism.

scholarly journals Effects of Petroleum-Based Oils as Dispersing Aids on Physicochemical Characteristics of Magnetorheological Elastomers

Materials ◽  
2021 ◽  
Vol 14 (22) ◽  
pp. 7026
Author(s):  
Norizatie Muhammad Zaki ◽  
Nurul Azhani Yunus ◽  
Muhamad Shakir Yusoff ◽  
Saiful Amri Mazlan ◽  
Siti Aishah Abdul Aziz ◽  
...  
Keyword(s):  
Magnetic Particles ◽  
Physicochemical Characteristics ◽  
Magnetorheological Elastomers ◽  
Weight Percentage ◽  
Chemical Structures ◽  
Microstructure Observation ◽  
Curing Characteristics ◽  
Similar Chemical ◽  
Low Performance ◽  
Light Mineral

This paper investigated the effects of petroleum-based oils (PBOs) as a dispersing aid on the physicochemical characteristics of natural rubber (NR)-based magnetorheological elastomers (MREs). The addition of PBOs was expected to overcome the low performance of magnetorheological (MR) elastomers due to their inhomogeneous dispersion and the mobility of magnetic particles within the elastomer matrix. The NR-based MREs were firstly fabricated by mixing the NR compounds homogeneously with different ratios of naphthenic oil (NO), light mineral oil (LMO), and paraffin oil (PO) to aromatic oil (AO), with weight percentage ratios of 100:0, 70:30, 50:50, and 30:70, respectively. From the obtained results, the ratios of NO mixed with low amounts of AO improved the material physicochemical characteristics, such as thermal properties. Meanwhile, LMO mixed the AO led to the best results for curing characteristics, microstructure observation, and magnetic properties of the MREs. We found that the LMO mixed with a high content of AO could provide good compatibility between the rubber molecular and magnetic particles due to similar chemical structures, which apparently enhance the physicochemical characteristics of MREs. In conclusion, the 30:70 ratio of LMO:AO is considered the preferable dispersing aid for MREs due to structural compounds present in the oil that enhance the physicochemical characteristics of the NR-based MREs.

Spectrofluorometric studies. VIII. The effect of CO2 and CHCl3 on the photochemistry of monofluorobenzene

1970 ◽  
Vol 48 (10) ◽  
pp. 1607-1613 ◽  
Author(s):  
M. E. MacBeath ◽  
I. Unger
Keyword(s):  
Quantum Yield ◽  
Quantum Yields ◽  
Vibrationally Excited ◽  
Excited Triplet ◽  
Improved Technique ◽  
Triplet Quantum Yields

The sensitized emission of biacetyl technique was used to study the effect of CHCl3 and CO2 on the triplet quantum yields of both benzene and monofluorobenzene.The monofluorobenzene was studied at λ excitation (λex) of 2470, 2590, and 2670 Å. At 2470 Å, the triplet yield increased by over 40% with both added gases; at λex 2590 Å, by around 30%; and at λex 2670 Å, about 20%. CHCl3 is slightly more effective than CO2 in enhancing the biacetyl phosphorescent yield. The quantum yield of fluorescence was unchanged with these added gases. Using a slightly improved technique, the comparison irradiation of a benzene–biacetyl mixture at λex 2540 Å with added CHCl3 was repeated. The results confirmed that the biacetyl phosphorescent yield decreased with increasing pressures of CHCl3, but suggest that the effect is not as great as previously reported. At the same wavelength, the triplet yield is unaffected by the addition of CO2. The quantum yield of fluorescence of benzene is virtually unaffected by the added gases. The data suggest that in the monofluorobenzene case the CO2 and CHCl3 are quenching vibrationally excited triplet fluorobenzene molecules.

Effect of aggregation of a cationic phthalocyanine in micelles and in the presence of human serum albumin

2006 ◽  
Vol 10 (01) ◽  
pp. 33-42 ◽  
Author(s):  
Myriam E. Rodriguez ◽  
Daniel A. Fernández ◽  
Josefina Awruch ◽  
Silvia E. Braslavsky ◽  
Lelia E. Dicelio
Keyword(s):  
Human Serum Albumin ◽  
Serum Albumin ◽  
Human Serum ◽  
Hydrophobic Interactions ◽  
Photophysical Properties ◽  
Sodium Dodecylsulfate ◽  
Water Soluble ◽  
Quantum Yields ◽  
Ionic Interactions ◽  
Triplet Quantum Yields

The photophysical properties of tetrakis(1,1-dimethyl-2-trimethylammonium)ethylphthalocyaninato zinc(II) tetraiodide (I) – a water-soluble cationic phthalocyanine – are presented in the presence of human serum albumin (HSA) and in micelles of sodium dodecylsulfate ( SDS ) and hexadecyltrimethylammonium chloride ( CTAC ). Spectrophotometric measurements showed that the surfactants SDS and CTAC induce monomerization of I, although the latter less efficiently than the former. This effect is less pronounced in the presence of HSA. The strength of this effect is evaluated through dimerization constants, which are Kd = (5 ± 1) × 105 m−1 in SDS , (1.5 ± 0.5) × 106 M −1 in CTAC , and (1.8 ± 0.9) × 106 M −1 in HSA. Fluorescence experiments confirm that aggregation of I drops as the concentration of surfactant is raised. Triplet quantum yields also decreased upon aggregation and were Φ T = 0.59, 0.16, and < 0.01 in SDS , CTAC , and HSA, respectively. These results indicate that the affinity of I for the environment is not just due to ionic interactions; hydrophobic interactions play an equally important role.

LASER INTENSITY AND THE COMPARATIVE METHOD FOR DETERMINATION OF TRIPLET QUANTUM YIELDS

1978 ◽  
Vol 28 (2) ◽  
pp. 277-281 ◽  
Author(s):  
R. Bensasson ◽  
C. R. Goldschmidt ◽  
E. J. Land ◽  
T. G. Truscott
Keyword(s):  
Laser Intensity ◽  
Comparative Method ◽  
Quantum Yields ◽  
Triplet Quantum Yields
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