Hydrophilic cyanine dyes as contrast agents for near-infrared tumor imaging: synthesis, photophysical properties and spectroscopic in vivo characterization

We have synthesized a group of glucamine and gluosamine-substituted cyanine dyes structurally related to indocyanine green (ICG) and have characterized these compounds with regard to their potential as contrast agents for biomedical optical imaging. The compounds reported herein exhibit increased hydrophilicity and less plasma protein binding (< 50%), and are thus expected to have different pharmacokinetic properties compared with ICG. Furthermore, we measured enhanced fluorescence quantum yields (7-15%) in a physiological environment with respect to ICG. For the derivative with the highest hydrophilicity (5a) the efflux from tumor and normal tissue was monitored by intensity-modulated diffuse optical spectroscopy after intravenous injection into tumor-bearing rats. In comparison with ICG, 5a exhibited a considerably enhanced tissue-efflux half-life (73 min versus less than 10 min for ICG in tumor tissue), a two-fold higher initial tissue absorption coefficient compared to ICG, and finally, it generated an elevated tumor-to-tissue concentration gradient up to 1 h after injection. In conclusion, compounds such as 5a are promising contrast agents for optical imaging, and could facilitate highly sensitive and specific detection of breast cancer or other malignancies by utilizing mechanisms similar to contrast-enhanced magnetic resonance imaging or computerized tomography.     

Fluorescence reabsorption in anthracene single crystals: Lifetime variations with emission wavelength and temperature

Fluorescence spectra and lifetimes of anthracene melt-grown single crystals and sublimation flakes have been examined at 298 and 77°K, using a mono-photon counting technique for the lifetime measurements. The observed emission decay times were nearly independent of the excitation wavelength, though a small dependence of the fluorescence spectrum on the excitation wavelength was noted. By contrast, large variations of fluorescence lifetimes in thick crystals were found as a function of emission wavelength. For thick melt-grown single crystals at 298°K the lifetime was found to increase from 9.8 nsec at 405 nm to 20.4 nsec at 445 nm. For sublimation flakes at 77°K and at 298°K and for thick melt-grown crystals at 77°K, the lifetimes were less than 10 nsec and were nearly independent of emission wavelength. Despite these relatively large variations in lifetimes, the decay rates at each separate wavelength remained exponential, within experimental error. Theoretical calculations were made of emission lifetimes based on a model with one reabsorbing state. The calculations are in substantial agreement with the experimental results.     

Optical properties of a polydiacetylene crystal: poly-[1,6-di(N-carbazolyl)-2,4-hexadiyne]

Normal incidence reflection spectra and Kramers-Kronig transforms are reported for a polydiacetylene crystal, DCHD (substituent group: N-carbazolymethyl). The lowest energy optical transition for the polymer backbone is found at 15 300 cm^?1, the lowest value obtained thus far for a polydiacetylene. The polymer chain and the carbazolyl substituent group may be treated as isolated chromophores - the former dominating the visible portion of the spectra and the latter dominating the UV portion. Polarization studies for the (001) and (10$\text{1}\text{?}$) faces of DCHD permit unambiguous assignment of the two lowest energy transitions in the carbazolyl group at 28 750 cm^?1 and 33 250 cm^?1 as short- and long-axis polarized, respectively.     

Raman and resonance-Raman spectra of CsI/I−3

Raman and resonance-Raman spectra of the I^?₃ ion isolated within CsI crystals have been studied using 647 nm and 488 nm exciting radiation. Sample temperatures between 300 and 20 K have been used. Eleven overtones of the symmetric stretching mode (nν₁) have been observed in the resonance-Raman spectrum excited by the 488 nm Ar⁺ laser line. Bands centred at 153, 170, 264 and 304 cm^?1 have been assigned as ν₃, 2ν₂, ν₁+ν₃ and 2ν₃(Σ⁺) respectively. The remaining structure between the nν₁ lines has been assigned as due to combinations of these lines with the lattice vibrations of the CsI crystal.     

Spectral Properties of the Cauchy Operator and Its Product with Bergman's Projection on a Bounded Domain

In this paper exact asymptotic formulae are found for singularvalues of the Cauchy operator and the logarithmic potentialtype operator (on a bounded domain), as well as their productswith Bergman's projection. It is shown that these spectral characteristicsdetect geometric properties of a domain (area and the lengthof the boundary). The hypothesis "can we hear the shape of adrum", from a paper by J.M. Anderson, D. Khavinson, and V. Lomonosov[‘Spectral properties of some integral operators arisingin potential theory’, Quart. J. Math. Oxford (2) 43 (1992)387-407], is correct in the above sense. 1991 Mathematics SubjectClassification: 47B10.     

Far downstream analysis for the Blasius boundary-layer stability problem

In this paper, we examine the large Reynolds number (Re) asymptoticstructure of the wave number in the Orr–Sommerfeld regionfor the Blasius boundary layer on a semi-infinite flat plategiven by Goldstein (1983, J. Fluid Mech., 127, 59–81).We show that the inclusion of the term which contains the leading-ordernon-parallel effects, at O(Re^{– 1/2}), leads to a non-uniformexpansion. By considering the far downstream form of each termin the asymptotic expansion, we derive a length scale at whichthe non-uniformity appears, and compare this position with theposition seen in plots of the wave number.     

The HITRAN 2008 molecular spectroscopic database

This paper describes the status of the 2008 edition of the HITRAN molecular spectroscopic database. The new edition is the first official public release since the 2004 edition, although a number of crucial updates had been made available online since 2004. The HITRAN compilation consists of several components that serve as input for radiative-transfer calculation codes: individual line parameters for the microwave through visible spectra of molecules in the gas phase; absorption cross-sections for molecules having dense spectral features, i.e. spectra in which the individual lines are not resolved; individual line parameters and absorption cross-sections for bands in the ultraviolet; refractive indices of aerosols, tables and files of general properties associated with the database; and database management software. The line-by-line portion of the database contains spectroscopic parameters for 42 molecules including many of their isotopologues.     

利用频域近红外光谱仪和磁共振谱仪测量骨骼肌能量代谢

利用频域近红外光谱技术(NIRS)可以实现生物组织光学参数的实时定量测量。由于生物组织的吸收系数与组织中的血红蛋白的合氧状态有关,使得频域近红外光谱技术可以用来无损测量肌肉组织中与能量代谢过程密切相关的氧气供应与消耗这个动态平衡过程。磷磁共振谱仪(31P-MRS)是无损检测骨骼肌能量代谢的金标准。为了研究细胞内pH值(pHi)对磷酸肌酸重新合成和氧合血红蛋白恢复过程的影响,作者利用频域NIRS和31P-MRS联合进行了健康成人的踝关节曲展(plantar flexion)实验。通过动脉阻断和长时间全力运动尽量降低肌肉组织细胞内pH值。对照结果表明,细胞环境酸化(pHi=6.42)明显地延长了运动停止后磷酸肌酸的重新合成和氧合血红蛋白的恢复过程。