共查询到20条相似文献,搜索用时 619 毫秒
1.
Laser-induced fluorescence spectroscopy was used to investigate -phenylethylamine molecules that were cooled via supersonic gas expansions. The bare molecule spectra reveal 0-0 transitions that can be attributed to four separate conformers. Upon the addition of water or alcohol solvents, a series of new peaks is induced that appear to be built off separate bare molecule transitions. This is a pattern that is markedly different from the one seen for solvent addition to tyramine, which includes an-OH in the para position. As a result, definite hypotheses can be made to explain the influence of the para-OH in affecting solvent induced conformations. 相似文献
2.
H and 13C NMR spectra were recorded for some novel picrate derivatives derived from 3,3-dimethyl-2,6-diarylpiperidin-4-ones and 3-benzyl-2,6-diarylpiperidin-4-one.
The photophysical properties of the picrate derivatives were studied in several solvents, which include a wide range of apolar,
polar and protic media. The observed lower fluorescence quantum yield may be due to an increase in the non-radiative deactivation
rate constant. This is attributed due to the presence of increased electrostatic interaction between N-protonated piperidone
ring and picryl anion ring so that the picryl anion ring lies perpendicular to the plane of the N-protonated piperidone ring
i.e., non co-planarity. Such a geometrical change in the excited state leads to an important Stokes shift, reducing the reabsorption
and reemission effects in the detected emission in highly concentrated solutions. The higher fluorescence quantum yield of
the picrate derivatives are observed in polar media. 相似文献
3.
We propose a concept of subchains for randomly branched polymers.As a direct application of this concept,the asymptotic expression of the average mean square radius of gyration is determined to give the fractal dimensions,in which the excluded volume effect is taken into consideration.Furthermore,we investigate a scaling relation that is associated with the Flory exponent υ,the fractal dimension df and the polydispersity exponent τ. 相似文献
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We investigate the translocation of single polymer chain through a nanopore located on a membrane with different solvents in the two sides of the membrane. For the case under study, the effect of solvents on the translocation dynamics is significant, and as a result, the mean first passage time shortens remarkably compared with that calculated in the case of good solvents on both the sides of the membrane. In addition, we also discuss the condition such that the present result holds true. 相似文献
6.
Time-dependent hybrid density functional theory in combination with Onsager reaction field model and super-molecular model has been applied to study solvent effects on the geometrical and electronic structures, as well as one/two-photon absorption properties, of 4-(N-(2-hydroxyethyl)-N-methyl)-amino-4'-nitroazobenzene. It is found that the short-range interaction has a large effect on the electronic structure of the solute molecule, namely, large red-shift of the maximum one-photon absorption is induced by hydrogen bonding. The solute molecule has a large two-photon absorption cross section, which is enhanced by the solvent effect. The computational results are in good agreement with measurements.[第一段] 相似文献
7.
J. Jayabharathi V. Kalaiarasi V. Thanikachalam K. Jayamoorthy 《Journal of fluorescence》2014,24(2):625-637
A set of π-expanded imidazole derivatives employing excited state intramolecular proton transfer (ESIPT) was designed and synthesized. The relationship between the structure and photophysical properties were thoroughly elucidated by comparing with the analogue blocked with ESIPT functionality. The compound possessing an acidic NH function as part of an intramolecular hydrogen bond system has much higher fluorescence quantum yield and Stokes shift and the π-expansion strongly influences the optical properties. The occurrence of ESIPT for imidazole tosylamide derivatives were less affected by the hydrogen-bonding ability of the solvents compared to the unprotected amine. The low pKa values for the monocation ? neutral equilibrium indicate the presence of intramolecular hydrogen bonding between the amino proton and tertiary nitrogen atom. 相似文献
8.
Solvent Suppression in Intermolecular Magnetic Resonance Spectra Multiple-Quantum Coherence Nuclear with Only z-axis Gradients 下载免费PDF全文
The solvent peak in the intermolecular multiple-quantum coherence spectra can be suppressed by either applying pulse field gradients or spinning sample along the magic angle direction (φ = 54.7). However, these two methods also suppress the signals of the solute. We design two pulse sequences with only z-axis gradients to suppress the solvent peak without reducing the intensity of solute signals. Compared to the former pulse sequence, the latter pulse sequence is insensitive to the imperfection of pulse flip angles. When the flip angles of the second pulse sequence are purposely deviated 1/10 from the optimal values, the solvent peak is still weak. Theoretical expressions, experimental observations and computer simulations demonstrate that the two methods can be used to effectively suppress solvent peak in intermolecular multiple-quantum coherence spectra. 相似文献
9.
Solvent effects on optical properties of a newly synthesized two-photon polymerization initiator: BPYPA 下载免费PDF全文
Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-(4-bromo-phenyl)-[4-(2-pyridin-4-yl-vinyl)phenyl]-amine (BPYPA). There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-(N, N-Di-n-butylamino)-p-stilbenyl vinyl] pyridine (DBASVP) reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements. 相似文献
10.
Solvent and electric field dependence of the photocurrent generation in donor:acceptor blend system 下载免费PDF全文
This paper reports that the blend films of poly
(2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV)
and N,N'-bis(1-ethylpropyl)-3,4: 9,10-perylene bis
(tetracarboxyl diimide) (EP-PDI) with the weight ratio of 1:2.5
have been prepared by spin-coating from chloroform (CF) and
chlorobenzene (CB) solutions respectively. The absorption
spectra and the morphology of the blend films show that large
crystal-like EP-PDI aggregates are formed in film prepared from
CB solution, which corresponds to a new absorption shoulder near
590nm, while there is no shoulder around 590\,nm in the
UV--Vis absorption spectra of the blend film from CF solution.
The electric-field dependence spectra of the photocurrent
generation quantum yield of the film from CB solution shows that
at weak electric field the EP-PDI aggregates act as more
efficient sensitizers, but at strong electric field the quantum
yields become almost invariable over the entire spectral range
no matter what the state of EP-PDI, monomer or aggregate. At
strong electric field, the photocurrent generation yields of
both films from CF and CB solution saturate and their yield
spectra become spectrally similar, mentioning that at strong
electric field the photoexcitons dissociate efficiently and the
free charges are collected by the electrodes almost completely. 相似文献
11.
Stepko A. S. Medvedeva A. A. Koshkin A. V. Lebedev-Stepanov P. V. 《Optics and Spectroscopy》2022,130(2):108-115
Optics and Spectroscopy - The solvatochromic shifts of the maxima of the absorption spectra of a 4-DASPI dye (4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide) in a water–ethylene glycol... 相似文献
12.
Guoqing Zhang Shin Han Kim Ruffin E. Evans Byeong Hyo Kim J. N. Demas Cassandra L. Fraser 《Journal of fluorescence》2009,19(5):881-889
A class of aryl trifluoromethyl-containing β-diketones were synthesized via one step Claisen condensation. These π-conjugated
diketones exhibit strong solvatochromism from intramolecular donor-acceptor charge transfer (CT). In addition, fluorescence
quantum yields (ϕf) and lifetimes (τf) were measured in different solvents. Diketones exhibit bathochromic shifts in emission spectra with increasing solvent polarity.
Fluorescence changes upon Group II metal binding were also studied. Despite the relatively simple structure, the anthracene-CF3 diketone, atm, has strong binding affinity for Mg2+. A 70 nm blue shift and sixfold increase in intensity were observed upon addition of only one equivalent MgCl2 in ethanol solution. It also shows selectivity for Mg2+ binding even in the presence of excess Ca2+. Association constant (Ka) calculations suggest atm has two orders of magnitude stronger chelation for divalent magnesium than for calcium. These findings
make atm an attractive starting point for molecular probe and light emitting material design. 相似文献
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《Journal of Macromolecular Science: Physics》2013,52(4):845-858
Abstract On the basis of three hypothesis: (1) ion association according to the mass action law, (2) no interchain association due to the same sort of charges on the chains, and (3) chain expansion owing to intrachain Coulombic repulsive force, a theoretical equation was derived to describe the viscosity behavior of a polyelectrolyte in a salt‐free polar solvent. The resulting equation fits well with experimental viscosity behavior of a polyelectrolyte solution in polar solvents. With some approximations, the equation leads to the Fuoss empirical equation. The effects of molecular weight, the average distance of two neighboring ionizable groups along the polymer chain, and the nature of the solvent on the polyelectrolyte conformation are discussed. 相似文献
15.
Absorption spectra of β-carotene in 31 solvents are measured in ambient conditions. Solvent effects on the 0-0 band energy, the bandwidth, and the transition moment of the S 0 → S 2 transition are analysed. The discrepancies between published results of the solvent effects on the 0-0 band energy are explained by taking into account microscopic solute-solvent interactions. The contributions of polarity and polarizability of solvents to 0-0 band energy and bandwidth are quantitatively distinguished. The 0-0 transition energy of the S 2 state at the gas phase is predicted to locate between 23000 and 23600 cm-1 . 相似文献
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《光谱学快报》2013,46(6):607-618
Abstract The enolisation tendencies of 1‐(o‐substituted phenyl)barbituric and ‐2‐thiobarbituric acid derivatives have been studied by observing the behaviour of the compounds in different solvents by 1H and 13C NMR. It has been found that the enolisation tendencies of the thiobarbituric acid derivatives observed in polar solvents are greater than those of the barbituric acid derivatives. The ratio of keto–enol tautomers of thiobarbituric acid derivatives in DMSO and in DMF has been calculated. 相似文献
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19.
High-Quality Large-Sized Single Crystals of Pb-Doped Bi2Sr2CuO6+δ High-To Superconductors Grown with Traveling Solvent Floating Zone Method 下载免费PDF全文
High quality Pb-doped Bi2Sr2Cu06+δ (Pb-Bi2201) single crystals are grown by the traveling solvent floating zone technique, with dimensions as large as - 50 min× - 5.0 min ×- 2 mm. The Pb-Bi2201 single crystals with different doping levels are obtained by the annealing process which covers a wide doping range of the overdoped region. We describe in detail the growth and annealing procedures and the characterization and physical property measurements of the Pb-Bi2201 crystals. The availability of these crystals provides a good opportunity to experimentally investigate high-To cuprate superconductors, particularly in the overdoped region. 相似文献
20.
N.R. Patil R.M. Melavanki S.B. Kapatkar K. Chandrasekhar N.H. Ayachit Siva Umapathy 《Journal of luminescence》2012,132(3):558-565
The fluorescence quenching studies of carboxamide namely (E)-N-(3-Chlorophenyl)-2-(3,4,5-trimethoxybenzylideneamino)-4,5,6,7 tetrahydrobenzo[b]thiophene-3-carboxamide [ENCTTTC] by aniline and carbon tetrachloride in six different solvents namely toluene, cyclohexane, n-hexane, n-heptane, n-decane and n-pentane have been carried out at room temperature with a view to understand the quenching mechanisms. The Stern–Volmer (S–V) plots have been found to be non-linear with a positive deviation for all the solvents studied. In order to interpret these results we have invoked the ground state complex formation and sphere of action static quenching models. Using these models various quenching rate parameters have been determined. The magnitudes of these parameters suggest that sphere of action static quenching model agrees well with the experimental results. Hence the positive deviation is attributed to the static and dynamic quenching. Further, with the use of Finite Sink approximation model, it was possible to check these bimolecular reactions as diffusion-limited and to estimate independently distance parameter R′ and mutual diffusion coefficient D. Finally an effort has been made to correlate the values of R′ and D with the values of the encounter distance R and the mutual coefficient D determined using the Edward's empirical relation and Stokes Einstein relation. 相似文献