Radiationless deactivation of hybridization-sensitive DNA probe

In this study we attempt to determine the deactivation mechanism of a hybridization-sensitive DNA probe by using steady state absorption and fluorescence spectroscopy. Thiazole orange or 2,2′-Methylenebis(N-alkylbenzothiazole) is covalently linked to a single nucleotide in the DNA probe. Radiationless deactivation of the fluorophores is mainly determined by photo-induced isomerization of the methine bridge. Experiments done using solutes of differing molecular weight (sucrose, glucose and glycerin) to provide solutions of similar viscosity reveals the importance of solution viscosity and fluorophore conformation on radiationless deactivation. The quantum yield of the fluorophore in high viscous solutions can be explained by a simple diffusion model. This linear relationship is broken when a dimer conformation of the fluorophore starts to form, which in turn influences the emission intensity of the fluorophore.     

Fluorescence Quantum Yield Determination of Propylparaben Using Flow Injection Spectroscopy

The determination of the fluorescence quantum yield of Propylparaben is introduced and applied to L-tyrosine as a standard by a new approach that can be applied to the pharmaceutical compound utilised in this study. The quantum yield is a critical figure of quality for the optical nature of a fluorophore. Numerous investigations have considered the glitter in both pharmaceutical and nature compounds for its medical and industrial significance. A straightforward method is detailed here to decide the quantum yield of Propylparaben in solution as an element of the fluorescence concentration. For this reason, L-Tyrosine is chosen as a fluorescence standard perspective to gauge the Propylparaben fluorescence quantum yield. The impacts of pH, solvents and flow rate on the assessment of quantum yield and quantum efficiency, for the reference and the solutions of Propylparaben, have been investigated. The results indicated that these parameters significantly influence the accuracy of the method. Diverse methods are concentrated on to represent distinctive quantum yield advancements with the quantum efficiency. The impact of these parameters was likewise considered. In this study, the application of the single method may be taken into consideration to compute quantum yield of Propylparaben, which was 0.36, and this is an exceptionally basic and general technique to solve the imperative issue of luminescence quantum yield assurance of other fluorescence compounds.     

Depth-resolved fluorescence measurement in a layered turbid medium by polarized fluorescence spectroscopy

We show that, when a turbid medium with a layered fluorophore distribution is excited by linearly polarized light, measurement of angle-resolved polarized fluorescence can provide depth-resolved fluorescence measurements.     

New Insights in the Interpretation of Tryptophan Fluorescence

Origin of tryptophan fluorescence is still up to these days a quiz which is not completely solved. Fluorescence emission properties of tryptophan within proteins are in general considered as the result of fluorophore interaction within its environment. For example, a low fluorescence quantum yield is supposed to be the consequence of an important fluorophore–environment interaction. However, are we sure that the fluorophore has been excited upon light absorption? What if fluorophore excitation did not occur as the result of internal conformation specific to the fluorophore environment? Are we sure that all absorbed energy is used for the excitation process? Fluorescence lifetimes of Trp residues are considered to originate from rotamers or conformers resulting from the rotation of the indole ring within the peptide bonds. However, how can we explain the fact that in most of the proteins, the two lifetimes 0.5 and 3 ns, attributed to the conformers, are also observed for free tryptophan in solution? The present work, performed on free tryptophan and tyrosine in solution and on different proteins, shows that absorption and excitation spectra overlap but their intensities at the different excitation wavelengths are not necessarily equal. Also, we found that fluorescence emission intensities recorded at different excitation wavelengths depend on the intensities at these excitation wavelengths and not on the optical densities. Thus, excitation is not equal to absorption. In our interpretation of the data, we consider that absorbed photons are not necessary used only for the excitation, part of them are used to reorganize fluorophore molecules in a new state (excited structure) and another part is used for the excitation process. A new parameter that characterizes the ratio of the number of emitted photons over the real number of photons used to excite the fluorophore can be defined. We call this parameter, the emission to excitation ratio. Since our results were observed for fluorophores free in solution and present within proteins, structural reorganization does not depend on the protein backbone. Thus, fluorescence lifetimes (0.5 and 3 ns) observed for tryptophan molecules result from the new structures obtained in the excited state. Our theory allows opening a new way in the understanding of the origin of protein fluorescence and fluorescence of aromatic amino acids.     

Vacuum Cherenkov effect in logarithmic nonlinear quantum theory

We describe the radiation phenomena which can take place in the physical vacuum such as Cherenkov-type shock waves. Their macroscopical characteristics - cone angle, flash duration, radiation yield and spectral distribution - are computed. It turns out that the radiation yield is proportional to the square of the proper energy scale of the vacuum which serves also as the vacuum instability threshold and the natural ultraviolet cutoff. While the analysis is mainly based on the theory engaging the logarithmic nonlinear quantum wave equation, some of the obtained results must be valid for any Lorentz-invariance violating theory describing the vacuum by (effectively) continuous medium in the long-wavelength approximation.     

A CTRW-based model of time-resolved fluorescence lifetime imaging in a turbid medium

We develop an analytic model of time-resolved fluorescent imaging of photons migrating through a semi-infinite turbid medium bounded by an infinite plane in the presence of a single stationary point fluorophore embedded in the medium. In contrast to earlier models of fluorescent imaging in which photon motion is assumed to be some form of continuous diffusion process, the present analysis is based on a continuous-time random walk (CTRW) on a simple cubic lattice, the objective being to estimate the position and lifetime of the fluorophore. This can provide information related to local variations in pH and temperature with potential medical significance. Aspects of the theory were tested using time-resolved measurements of the fluorescence from small inclusions inside tissue-like phantoms. The experimental results were found to be in good agreement with theoretical predictions provided that the fluorophore was not located too close to the planar boundary, a common problem in many diffusive systems.     

Spatial quantum correlations in multiple scattered light

We predict a new spatial quantum correlation in light propagating through a multiple scattering random medium. The correlation depends on the quantum state of the light illuminating the medium, is infinite in range, and dominates over classical mesoscopic intensity correlations. The spatial quantum correlation is revealed in the quantum fluctuations of the total transmission or reflection through the sample and should be readily observable experimentally.     

硫杂杯[4]芳烃基胶束自组装荧光探针的结构性质及检测性能的研究

水体中重金属污染因威胁生态环境和人类健康而被受广泛关注。荧光探针由于具有快速高效检测重金属的特性,一直是该领域的研究热点。通常,荧光探针在结构上包括对待测物质起识别作用的受体和能产生信号响应的荧光体,并逐步形成了内在型、共轭型、系综型和模板辅助自组装型等四种结构类型。近年来,基于受体和荧光体在表面活性剂胶束内自组装而形成的胶束自组装型荧光探针因结构简单、易于制备、能直接应用于水环境等特点逐渐受到重视。以对铜离子具有优异结合性能的对叔丁基硫杂杯[4]芳烃（TCA）为受体,以芘、荧蒽、蒽、菲、苝等分子为荧光体,通过表面活性剂胶束自组装制备针对Cu2+检测的胶束自组装型荧光探针,采用参比法测定了胶束自组装荧光探针的荧光量子产率,采用稳态荧光法测定了胶束聚集数,同时通过计算荧光猝灭率分别考察了荧光体种类、复配表面活性剂等因素对该探针的Cu2+检测性能的影响情况。实验结果显示,采用十二烷基硫酸钠（SDS）、曲拉通100（TX-100）、聚氧乙烯月桂醚（Brij35）等三种不同的表面活性剂对探针荧光体的荧光量子产率产生了明显影响,测得的荧光探针荧光量子产率介于0.25~0.47,且三者逐渐增大,说明表面活性剂改变了胶束内荧光分子芘所处微环境的极性,且不同类型表面活性剂对微环境极性的影响程度有所差异,微环境极性的增强对极性更大的激发态芘具有更强的稳定作用。而受体TCA的加入对荧光体所处微环境极性影响较小,未对荧光量子产率产生较大影响。但TCA的加入使探针的胶束聚集数明显减少,这归因于具有两亲性的受体TCA分子通过胶束自组装进入并分散在表面活性剂分子层中,形成共胶束结构,从而改变了表面活性剂分子的聚集状态。荧光体变更对荧光探针的Cu2+检测性能有显著影响,在同样条件下,以荧蒽、蒽、菲作为荧光体的探针检测Cu2+所得到的荧光猝灭率远高于芘、苝,这主要是因为不同荧光体在从激发态返回基态时辐射跃迁所释放能量不同,其能量与受体TCA识别Cu2+所需能量之间的匹配度越高,荧光猝灭率越大。不同类型的表面活性剂之间的复配能明显提升荧光探针检测性能,当非离子/阴离子、非离子/阳离子型复配表面活性剂之间的复配比例分别为7∶3和1∶1时荧光猝灭率达到最大值,且均高于单一表面活性剂时的荧光猝灭率。这说明不同类型表面活性剂复配的最佳比例存在较大差异,但均有效地增强了受体与荧光体的分散性及自组装性能,提高了对Cu2+的检测性能。研究结果将为新型胶束自组装荧光探针的设计和应用提供数据参考。     

Kerr相互作用下量子相干性分布和量子信息流动

本文针对Kerr相互作用下系统中量子相干性的动力学分布进行了研究.所讨论系统包含两个没有相互作用的原子,每个原子都被囚禁在各自的光腔中,同时光腔被充满了非线性Kerr介质.研究发现非线性Kerr相互作用能够增加两原子间的量子相干性,而且增大的幅度会随着Kerr相互作用强度的增加而得以提高.其次,借助迹距离的方法,还探讨了非线性Kerr相互作用对于原子与光腔之间的量子信息流动的影响,发现Kerr相互作用可以加快量子信息回流到原子子系统中,抑制原子子系统与其余子系统间的量子信息交换,阻碍量子信息在系统中不同子系统间的流动,从而保护原子子系统中拥有的量子信息.     

Photophysical properties of tris-methoxycoumarin derivative of a cryptand

The paper reports the photophysical studies of a macrobicyclic cryptand where the three secondary amino nitrogen have been derivatized with methoxy coumarin in various solvents at room temperature and at 77 K. The system having (F-S)₃-R configuration (where F is fluorophore, S is CH₂ spacer and R is receptor unit) shows intramolecular PET from the receptor nitrogen atoms of the cryptand moiety to the coumarin units reducing the fluorescence quantum yield and lifetime of coumarin in the ligand. However, the fluorescence intensity is enhanced in presence of protons and Zn⁺² ion in dry THF medium. Metal ions like Cu(II) and Co(II) quench the fluorescence. Presence of protons induces a greater enhancement of emission intensity implying all the nitrogen lone pairs responsible for PET are protonated. Another interesting feature of this ligand is that it exhibits room temperature phosphorescence (RTP) apart from exhibiting PET. The observation of RTP has not been reported earlier for any other coumarin derivative.     

Live Cell Imaging With Biocompatible Fluorescent Carbon Quantum Dots Derived From Edible Mushrooms Agaricus bisporus,Pleurotus ostreatus,and Suillus luteus

In the study, fluorescent imaging of live cells was performed using fluorescent carbon quantum dots derived from edible mushrooms species; Agaricus bisporus, Pleurotus ostreatus, and Suillus luteus as a fluorophore agent. Carbon quantum dots were synthesized through a facile and low-cost method based on microwave irradiation of dried mushroom samples in hydrogen peroxide solution under optimized conditions (microwave energy, solution type, duration of microwave treatment, amount of mushroom). Upon purification with centrifugation, microfiltration, and dialysis, the lyophilized carbon quantum dots were identified through UV–visible, fluorescence and FT-IR, X-ray photoelectron spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy, and quantum yield calculation. Cell viability assessment of the carbon quantum dots was evaluated against human epithelial cell line PNT1A using the Alamar Blue Assay. In vitro fluorescence cell imaging studies demonstrated that the carbon dots could dynamically penetrate the cell membrane and nuclear membrane and localize in both the cytoplasm and the nucleus.

     

小分子荧光探针的光谱

运用紫外-可见光谱、荧光光谱法研究了以二烯酮为荧光团的1,5-双(4-羟基)-1,4-戊二烯-3-酮探针的光学性质.一系列pH滴定实验表明探针的紫外吸收和荧光光谱随溶液的pH值的改变而变化.同时,探针紫外吸收光谱发生明显的红移,荧光光谱强度也随之变化,在碱性条件下,相对荧光强度浮动较大.解离常数pK<,α>为9.25,...     

A Highly Selective Fluorescent Probe for Detection of Biological Samples Thiol and Its Application in Living Cells

Probe 1 was designed and synthesized as a new fluorescent molecular probe for thiols in PBS buffer at physiological condition. This fluorescent molecular probe consists of a thiol reaction moiety bound to a coumarin fluorophore. Its fluorescence quantum yield is low, but a drastic enhancement of fluorescence intensity was observed in the presence of thiols. Possible interference with other analytes was examined. Probe 1 displays a highly selective fluorescent enhancement with thiols, and the probe was successfully applied to thiols determination in intracellular, in human urine and blood samples.     

Security of decoy states QKD with finite resources against collective attacks

The number of transmitted signals in practical quantum key distribution (QKD) protocol is always finite. We discuss the security of decoy states QKD protocol with finite resources by considering the statistical fluctuation for the yield and error rate of the quantum state in different sources of pulses (signal sources and decoy sources). The number of exchanged quantum signals vs positive key generation rate is given with experiment results.     

Perfect Transfer of Many-Particle Quantum State via High-Dimensional Systems with Spectrum-Matched Symmetry

The quantum state transmission through the medium of high-dimensional many-particle system (boson or spinless fermion) is generally studied with a symmetry analysis. We discover that, if the spectrum of a Hamiltonian matches the symmetry of a fermion or boson system in a certain fashion, a perfect quantum state transfer can be implemented without any operation on the medium with pre-engineered nearest neighbor (NN). We also study a simple but realistic near half-filled tight-binding fermion system with uniform NN hopping integral. We show that an arbitrary many-particle state near the fermi surface can be perfectly transferred to its translational counterpart.     

Perfect Transfer of Many-Particle Quantum State via High-Dimensional Systems with Spectrum-Matched Symmetry

The quantum state transmission through the medium of high-dimensional many-particle system （boson or spinless fermion） is generally studied with a symmetry analysis. We discover that, if the spectrum of a Hamiltonian matches the symmetry of a fermion or boson system in a certain fashion, a perfect quantum state transfer can be implemented without any operation on the medium with pre-engineered nearest neighbor （NN）. We also study a simple but realistic near half-filled tight-bindlng fermion system wlth uniform NN hopping integral. We show that an arbitrary many-particle state near the fermi surface can be perfectly transferred to its translational counterpart.     

Qudit state estimation with a fixed set of bases

We analyse the estimation of a pure d-dimensional quantum state with a finite number of measurements and compare several estimation schemes. In this paper we concentrate on consecutive von Neumann measurements on a finite number of identically prepared systems in dimensions d=2, d=4 and d=8. We propose two schemes with different types of fixed measurement directions. Inspired by integration theory our first approach uses the Halton sequence (a so-called quasi-Monte Carlo sequence) to obtain measurement directions (`sampling points') with high uniformity over the configuration space. Our second approach extends this idea and optimises the distribution of the measurement directions to yield a rather high fidelity in quantum state estimation. This optimisation results in a uniform distribution of the directions and large quantum distances between the directions. Furthermore we establish a link to mutually unbiased bases.     

Fluorescence Dynamics of Three UV-B Sunscreens

Polarity of the surrounding medium affects the excited states of UV-B sunscreens. Therefore understanding excited state processes in a mixed polarity model system similar to skin is essential. We report the excited state lifetimes, quantum yields, radiative and non-radiative rates of three sunscreens. Among the three UV-B sunscreens studied, octyl salicylate emits from a single excited state, while padimate O and octyl methoxy cinnamate show multiple states. The radiative rates of salicylate and cinnamate are approximately constant, while that of padimate O depends strongly on solvent. The non-radiative rates of all sunscreens vary with solvent polarity. Compared to salicylate and cinnamate, padimate O is complex to analyze because of its two emission peaks and one peak’s strong dependence on the dielectric constant. High absorbance, broad absorption peak with small fluorescence quantum yield, and low radiative rate make octyl methoxy cinnamate a superior UV-B sunscreen ingredient. The complexity in excited-state analysis shows that the lifetimes of the sunscreens are critical parameters, in addition to absorbance and quantum yield. Fluorescence lifetime substantiates the use of polystyrene nanospheres as a model host to study the photo-physical properties of sunscreen in a heterogeneous environment.     

Behaviour of Fluorescence Emission of Cyanine Dyes,Cyanine Based Fluorescent Nanoparticles and CdSe/ZnS Quantum Dots in Water Solution Upon Specific Thermal Treatments

Fluorescence techniques are widely used as detection methods in a wide range of biological imaging and analytical applications. The purpose of this work is to determine a measurement method which leads to a comparison between different classes of fluorophores in term of stability of the fluorescence signal upon thermal treatment cycles. This kind of investigation can determine whether the fluorophore performance is affected by heating/cooling cycles and to what extent. The fluorophores considered in this work were organic fluorophores belonging to the family of indocyanine dyes (IRIS3 by Cyanine Technologies S.p.A.) in their molecular form or encapsulated within silica nanoparticles, and CdSe/ZnS carboxyl quantum dots (Qdots 565 ITK by Invitrogen). The NIST Standard Reference Material® SRM 1932 fluorescein solution was used in the certified concentration as reference material in order to evaluate the repeatability of the used spectrofluorimeter. The proposed measurement protocol allows to characterize all kind of fluorophores upon thermal treatments. This allows direct comparison of their performance under temperature changes, giving useful guidelines for the selection of the most suitable fluorophore for the envisaged application. Moreover the method appears to be a promising tool for the characterisation of reference fluorescent materials. The experimental results demonstrate that each fluorophore class shows a specific behaviour. The experimental data analysis points out an important hysteresis effect for quantum dots that was not detected for cyanine molecules and was only slightly detected for cyanine doped silica nanoparticles.     

Ultrafast resonance energy transfer in bio-molecular systems

In this article, we present our consistent efforts to explore thedynamical pathways of the migration of electronic radiation by usingultrafast (picosecond/femtosecond time scales) Förster resonance energytransfer (FRET) technique. The ultrafast non-radiative energy migration froman intrinsic donor fluorophore (Tryptophan, Trp214) present in domain IIA ofa transporter protein human serum albumin (HSA) to variousnon-covalently/covalently attached organic/inorganic chromophores includingphotoporphyrin IX (PPIX), polyoxovanadate[V₁₅As₆O₄₂(H₂O)]^-6clusters (denoted as V₁₅) and CdS quantum dots (QDs) has beenexplored. We have also used other covalently/non-covalently attachedextrinsic fluorogenic donors (NPA, ANS) in order to exploit the dynamics ofresonance energy migration of an enzyme α-chymotrypsin (CHT). Theuse of extrinsic donor instead of intrinsic Trp in CHT avoids ambiguity inthe location of the donor molecule as seven tryptophans are present in theenzyme CHT. We have labeled CHT with ANS (1-anilinonaphthalene-8-sulfonate)and NPA (4-nitrophenyl anthranilate) and studied FRET. Labeling of DNA hasalso been done in the context that the DNA bases have very low quantum yieldfor fluorescence. We have also validated FRET model over nano-surface energytransfer technique (NSET) in the case of quantum clusters and applied thefindings to other QDs. The use of QDs over organic fluorophore was justifiedby least photo-bleaching of QDs compared to organic fluorophore. Our studiesmay find relevance in the exploration of alternate pathway for ultrafastmigration of electronic radiation through FRET to minimize the detrimentaleffect of UV radiation in living organism.