Excited‐state structural dynamics and vibronic coupling of 1,3‐dithiole‐2‐thione—resonance Raman spectroscopy and density functional theory calculation study

1,3‐Dithiole‐2‐thione (DTT) was synthesized and characterized using NMR, FT‐Raman, FT‐IR, UV spectroscopies. Resonance Raman spectra (RRs) were obtained with 341.5, 354.7 and 368.9 nm excitation wavelengths and density functional calculations were done to elucidate the electronic transitions and the RRs of DTT in cyclohexane solution. The RRs indicate that the Franck‐Condon region photodynamics is predominantly along the CS stretch+ H‐CC‐H scissor υ₄, accompanied by the H‐CC‐H scissor υ₃, S‐C‐S symmetric stretch υ₆, CC stretch υ₂, and overtone of the non‐totally symmetric SC‐S2 out‐of‐plane deformation 2υ₁₁. The excited‐state dynamics and the force constant of CS stretch calculated by the RRs were discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Multi-band infrared CO2 absorption sensor for sensitive temperature and species measurements in high-temperature gases

A continuous-wave laser absorption diagnostic, based on the infrared CO₂ bands near 4.2 and 2.7 μm, was developed for sensitive temperature and concentration measurements in high-temperature gas systems using fixed-wavelength methods. Transitions in the respective R-branches of both the fundamental υ ₃ band (~2,350 cm^?1) and combination υ ₁ + υ ₃ band (~3,610 cm^?1) were chosen based on absorption line-strength, spectral isolation, and temperature sensitivity. The R(76) line near 2,390.52 cm^?1 was selected for sensitive CO₂ concentration measurements, and a detection limit of <5 ppm was achieved in shock tube kinetics experiments (~1,300 K). A cross-band, two-line thermometry technique was also established utilizing the R(96) line near 2,395.14 cm^?1, paired with the R(28) line near 3,633.08 cm^?1. This combination yields high temperature sensitivity (ΔE” = 3,305 cm^-1) and expanded range compared with previous intra-band CO₂ sensors. Thermometry performance was validated in a shock tube over a range of temperatures (600–1,800 K) important for combustion. Measured temperature accuracy was demonstrated to be better than 1 % over the entire range of conditions, with a standard error of ~0.5 % and µs temporal resolution.     

Carbon Dioxide Measurement Based on Multimode Diode Laser Correlation Spectroscopy Employing Wavelength Modulation Techniques

The use of a tunable multimode diode laser system based on correlation spectroscopy and wavelength modulation spectroscopy to measure the concentration of the carbon dioxide in ambient air through the 2 υ₁ + 2υ₂ + υ₃ absorption lines around 1570 nm is reported. The carbon dioxide concentrations are derived from the relationship between the normalized second-harmonic signal peak heights of the measurement and reference signals. The validation of the system is conducted by a set of experiments with controlled carbon dioxide and nitrogen mixtures. The correlation and standard deviation between the measured and actual carbon dioxide concentrations are 0.9973 and 4.03%, respectively, over the tested range. A detection limit of 340 ppm m was achieved using 30 successive measurements during 30 min. All these results demonstrated potential utility of the system for carbon dioxide sensing.     

Impact of NIR wavelength lighting in image acquisition on finger vein biometric system effectiveness

Finger vein biometric systems become increasingly more popular because they offer higher security comparing to other authentication solutions with respect to positive persons experience. Those systems operate on near infrared light (NIR) in wavelength range from around 700 to 1000 nm, however dedicated research to determine impact of NIR lighting on biometric system effectiveness has not been conducted and presented in the literature ever before. In this paper the study of correlation between wavelengths in NIR spectra and effectiveness of person identification in a biometric system is presented. To achieve that goal, a new model of image acquisition system allowing change of light wavelengths has been created and NIR finger vein dataset containing 11 556 images was established. Furthermore, this model was used to perform experimental work and proof that some NIR wavelengths better suit for vein patterns acquisition, allowing to increase the recognition effectiveness of finger vein biometric systems.     

Absorption and quantitative characteristics of C-H bond and O-H bond of NIR

The previous study mainly focused on the interpretation of the relationship between absorption characteristics and quantitative contribution in each near-infrared (NIR) frequency range. Furthermore, the absorption characteristics of NIR mainly cover overtones and combinations of molecular vibrations such as CH, OH, SH, and NH bonds. And it has been know that NIR wavelengths of C-H bond and O-H bond are assigned to different radio frequencies. This paper was intended to investigate the absorption characteristics of bond C-H and O-H bonds in NIR spectral range. Water and acetone which correspond to O-H and C-H bonds have been selected as typical solvents, as well as solutes. Calibration models were established using partial least square regression (PLS) and multiple linear regression (MLR). The parameter of the model were optimized by different spectral pretreatment methods. The result showed that the model set by Savitzky-Golay smooth (SG) in the spectral region of 810–1100 nm could successfully make accurate predictions. Short wave-NIR region has been discovered as optimum characteristic absorption of C-H and O-H bonds.     

Gold nanoflowers with mesoporous silica as “nanocarriers” for drug release and photothermal therapy in the treatment of oral cancer using near-infrared (NIR) laser light

In this experiment, we successfully developed nanocarriers in the form of gold nanoflowers coated with two layers of silica for the purposes of drug loading and NIR (near-infrared) photothermal therapy for the treatment of oral cancer. The gold nanoflowers converted NIR laser energy into heat energy. The cores were coated with a thin silica layer (AuNFs@SiO₂) to protect the gold nanoflowers from intraparticle ripening. The second layer was mesoporous silica (AuNFs@SiO₂@mSiO₂), which acted as a nanocarrier for anticancer drug (DOX) loads. The mean effective diameter of the nanoparticles was approximately 150–200 nm, whereas the peak absorption of the AuNFs was 684 nm. After the AuNFs were encapsulated by the silica shells, the plasmonic absorption peak of AuNFs@SiO₂ and AuNFs@SiO₂@mSiO₂ exhibited a red shift to 718 nm. When exposed to an 808 nm NIR laser, these crystals showed an obvious photothermal conversion in the NIR region and a highly efficient release of DOX. Biocompatibility was assessed in vitro using Cell Counting Kit-8 assays, and the results showed that the nanocarriers induced no obvious cytotoxicity. This nanomaterial could be considered a new type of material that shows promising potential for photothermal-chemotherapy against malignant tumours, including those of oral cancers.     

Effect of sintering temperature of Ce<Superscript>3+</Superscript>-doped Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> phosphors on light emission and properties of crystal structure for white-light-emitting diodes

The effect of the sintering temperature of Ce³⁺-doped Lu₃Al₅O₁₂ (Ce-LuAG) phosphors on the emission and properties of the crystal structure was studied. A cathodoluminescence peak at 317 nm, which was assigned to lattice defects, was exhibited in addition to emission peaks at 508 and 540 nm for the Ce-LuAG phosphors. The intensities of the 317 nm emission peak for the phosphors with mean particle diameters of 5.0 and 10.0 µm formed at a low sintering temperature of 1430 °C were higher than those for the phosphors with mean particle diameters of 18.0 and 20.5 µm formed at a high sintering temperature of 1550 °C. In contrast, the electroluminescence spectra for fabricated white-light-emitting diodes (LEDs) using the phosphors revealed that the intensity of the peak at 540 nm was strong for the mean particle diameters of 18.0 and 20.5 µm. The intensity of the 540 nm peak, which is attributed to the 4f→5d transition of the Ce³⁺ activator, showed a dependence on the sintering temperature. The relationship between the optical properties and the lattice defects is discussed.     

Mid-infrared supercontinuum generation in a four-hole As2S5 chalcogenide microstructured optical fiber

We demonstrate the supercontinuum (SC) generation in a four-hole As₂S₅ chalcogenide microstructured optical fiber (MOF) experimentally. The As₂S₅ glass has better property of transmission than As₂S₃ glass in the visible range. The four-hole As₂S₅ MOF is fabricated by a rod-in-tube method. The SCs generated by different pump wavelengths at 2,000, 2,300 and 2,500 nm in the MOF whose length is from 2.3 to 20 cm are demonstrated. Those pump wavelengths correspond to the chromatic dispersion wavelength in the normal chromatic dispersion region, the anomalous chromatic dispersion region close to zero-dispersion wavelength (ZDW) and the anomalous chromatic dispersion region far from ZDW, respectively. Wider SCs can be obtained when pumped at a wavelength in the anomalous dispersion region close to ZDW. The widest SC range of 4,280 nm (from 1,370 to 5,650 nm) covering two octaves was obtained in a 4.8-cm-long fiber pumped at 2,300 nm.     

Femtosecond optical nonlinearity of Au nanoparticles under their excitation in nonresonant relative to surface plasmon conditions

Nonlinear optical response of Au island films to femtosecond laser pulses is studied in the vicinity but not exactly at the surface plasmon absorption peak (λ _spr = 560 nm). The third-order nonlinear optical susceptibility is shown to be Reχ ⁽³⁾ = +1.7 × 10^?7 esu and Reχ ⁽³⁾ = +1 × 10^?7 esu at the wavelengths 800 and 460 nm, respectively. Kinetics of the optical nonlinear response has been studied for wavelengths 400 and 800 nm. It is believed that the origin of nonlinearity at the wavelengths is related to the free-electron heating in the conduction band and their further thermalization via electron–electron scattering, but at 400 nm the contribution to the nonlinear susceptibility because of interband d → s, p transitions is also possible.     

Multi-beam second-harmonic generation in beta barium borate with a spatial light modulator and application to internal structuring in poly(methyl methacrylate)

Parallel beam frequency doubling of 170 fs, NIR pulses is demonstrated by placing a thin beta barium borate (BBO) nonlinear crystal after a spatial light modulator. Computer-generated holograms applied to the spatial light modulator create 18 parallel diffracted beams at the fundamental wavelength λ=775 nm, then frequency doubled to λ=387 nm and focussed inside the poly(methyl methacrylate) (PMMA) substrate for refractive index structuring. This procedure, demonstrated for the first time in PMMA, requires careful attention to phase matching of multiple beams and opens up dynamic parallel processing at UV wavelengths where nematic liquid crystal devices are more sensitive to optical damage. By overlapping filamentary modifications, an efficient, stable volume phase grating with dimensions 5×5×2.0 mm³ and pitch Λ=15 μm was fabricated in 18 minutes and reached a first-order diffraction efficiency of 70 % at the Bragg angle.     

Bay Functionalized Perylenediimide with Pyridine Positional Isomers: NIR Absorption and Selective Colorimetric/Fluorescent Sensing of Fe<Superscript>3+</Superscript> and Al<Superscript>3+</Superscript> Ions

Bay functionalized perylene diimide substituted with pyridine isomers, (2-pyridine (2HMP-PDI), 3-pyridine (3-HMP-PDI) and 4-pyridine (4-HMP-PDI)) have been synthesized and explored for selective coloro/fluorimetric sensing of heavy transition metal ions. HMP-PDIs showed strong NIR absorption (760–765 nm) in DMF. The absorption and fluorescence of HMP-PDIs have been tuned by make use of pyridine isomers. Reddish-orange color was observed for 2-HMP-PDI (λ_max = 437, 551, 765 nm) whereas 4-HMP-PDI exhibited light green (λ_max = 432, 522, 765 nm). 3-HMP-PDI showed orange-yellow (λ_max = 431, 524, 762 nm). The fluorescence spectra of 2-, 3- and 4-HMP-PDI showed λ_max at 585, 538, 546 nm, respectively. Interestingly, HMP-PDI dyes showed selective color change (intense pink color) and fluorescence quenching for Fe³⁺ and Al³⁺ metal ions in DMF. Absorbance spectra revealed complete disappearance of NIR absorption and intensification/appearance of new peak at lower wavelength. The concentration dependent studies suggest that 4-HMP-PDI can detect up to 36.52 ppb of Fe³⁺ and 43.12 ppb of Al³⁺ colorimetrically. The interference studies in presence of other metal ions confirmed the good selectivity for Fe³⁺ and Al³⁺. The mechanistic studies indicate that Lewis acidic character of Fe³⁺ and Al³⁺ ions were responsible for selective color change and fluorescence quenching.     

Determination of Microamounts of Proteins by Resonance Light Scattering with Copper Phthalocyanine Tetrasulfonic Acid

Abstract

Based on the strong enhancement effect of proteins on the resonance light scattering of copper phthalocyanine tetrasulfonic acid, a method for the determination of microamounts of proteins has been developed. Under the experimental conditions (2.0×10^?6 mol/L copper phthalocyanine tetrasulfonic acid, pH 2.60, ionic strength 0.001 mol/L NaCl), the linear range of this assay is 0.06–4.0 µg/mL for bovine serum albumin (BSA), 0.1–2.0 µg/mL for human serum albumin (HSA), 0.0–2.0 µg/mL for human γ‐IgG, and 0.2–6.0 µg/mL for ovalbumin. The detection limits (3δ) are 16.8 ng/mL for BSA, 23.4 ng/mL for HSA, 37.6 ng/mL for human γ‐IgG, and 48.3 ng/mL for ovalbumin, respectively. This method has been applied to the analysis of total proteins in human serum samples collected from the hospital, and the results were in good agreement with those reported by the hospital.     

基于近红外光谱的北方潮土土壤参数实时分析

选取中国北方潮土作为研究对象,探索利用近红外光谱分析技术分析土壤参数的可行性和可能性。从一块试验麦田共采集了150个土样,土样在采集回试验室后,在保持其原始状态的条件下利用傅里叶变换近红外光谱仪迅速测定了其近红外光谱。近红外光谱变量为原始吸收光谱和一阶微分光谱,分析的土壤参数有土壤水分、有机质和全氮的含量。对于土壤水分,在相关分析的基础上建立了一元线性模型,所采用的波长为1 920 nm,模型的相关系数达到0.937,模型可以直接用于土壤水分的实时预测。对于有机质和全氮含量建立了多元回归模型,有机质预测模型所采用的波长是1 870和1 378 nm,全氮预测模型所采用的波长则是2 262和1 888 nm。分析结果表明土壤有机质和全氮含量可以利用田间土样的近红外光谱特性进行分析和检测,建立的线性模型是有效的。     

Aqueous Photophysical Parameters of Congo Red

Using steady-state fluorescence spectroscopy and UV-Vis absorbance spectrometry, the salient photophysical parameters of Congo red, a very important biological staining reagent, was determined. Its absorbance was observed at 497.0 nm; its molar absorptivity ε was determined as 6.26 × 10⁴ M–cm. Its fluorescence, when excited at 330.0 nm, was observed at 417.0 nm. The quantum yield, ф, in aqueous solution was determined by two different methods—the relative, or comparative, method and the absolute method. Both methods gave the same value of 0.011. The room temperature fluorescence lifetime τ_o was determined as 2.8 ns using the Strickler–Berg equation.     

Optical Detection of Some Hydrazine Compounds Based on the Surface Plasmon Resonance Band of Silver Nanoparticles

An indirect colorimetric method is presented for spectrophotometric determination of hydrazine, phenylhydrazine, and isoniazid. Reduction of silver ions to silver nanoparticles (AgNPs) by these analytes as active reducing agents in the presence of polyvinylpyrrolidone (PVP) and also cetyltrimethylammonium chloride (CTAC) as a stabilizer is the basis of the proposed method. The changes in plasmon absorbance of the AgNPs at λ = 415 nm in the presence of PVP were proportional to concentration of hydrazine, phenylhydrazine, and isoniazid in the ranges of 4.0–150.0 µM, 1.0–55.0 µM, and 2.0–30.0 µM, respectively, and the detection limit obtained was 0.79 µM. In the presence of CTAC, the linear ranges were 0.5–10.0 and 10.0–300.0 µM for hydrazine, 1.0–40.0 µM for phenylhydrazine, and 0.2–10.0 and 10.0–90.0 µM for isoniazid, and the detection limit was 0.12 µM. The method has been applied for determination of these analytes in different real samples such as boiler feed water and tablet.     

Fluorescence Anisotropy of Tyrosinate Anion Using One-, Two- and Three-Photon Excitation

We examined the emission spectra and steady-state anisotropy of tyrosinate anion fluorescence with one-photon (250–310 nm), two-photon (570–620 nm) and three-photon (750–930 nm) excitation. Similar emission spectra of the neutral (pH 7.2) and anionic (pH 13) forms of N-acetyl-L-tyrosinamide (NATyrA) (pK_a 10.6) were observed for all modes of excitation, with the maxima at 302 and 352 nm, respectively. Two-photon excitation (2PE) and three-photon excitation (3PE) spectra of the anionic form were the same as that for one-photon excitation (1PE). In contrast, 2PE spectrum from the neutral form showed ~30-nm shift to shorter wavelengths relative to 1PE spectrum (λ_max 275 nm) at two-photon energy (550 nm), the latter being overlapped with 3PE spectrum, both at two-photon energy (550 nm). Two-photon cross-sections for NATyrA anion at 565–580 nm were 10 % of that for N-acetyl-L-tryptophanamide (NATrpA), and increased to 90 % at 610 nm, while for the neutral form of NATyrA decreased from 2 % of that for NATrpA at 570 nm to near zero at 585 nm. Surprisingly, the fundamental anisotropy of NATyrA anion in vitrified solution at ?60 °C was ~0.05 for 2PE at 610 nm as compared to near 0.3 for 1PE at 305 nm, and wavelength-dependence appears to be a basic feature of its anisotropy. In contrast, the 3PE anisotropy at 900 nm was about 0.5, and 3PE and 1PE anisotropy values appear to be related by the cos⁶ θ to cos² θ photoselection factor (approx. 10/6) independently of excitation wavelength. Attention is drawn to the possible effect of tyrosinate anions in proteins on their multi-photon induced fluorescence emission and excitation spectra as well as excitation anisotropy spectra.     

Dual-wavelength CW diode-end-pumped a-cut Nd:YVO4 laser at 1064.5 and 1085.5 nm

A simple and compact dual-wavelength continuous wave (CW) laser-diode end-pumped laser operating simultaneously at 1,064.5 and 1,085.5 nm in a single a-cut Nd:YVO₄ has been demonstrated. We have used two Nd:YVO₄ crystals with different Nd⁺³ concentrations and lengths; 0.1 %-14 mm and 0.25 %-12 mm. The maximum total output power of 5 and 6.18 W, including 1,064.5 and 1,085.5 nm, is achieved at the incident pump power of 22 and 18 W, with a slope efficiency 23.3 and 32.9 %, respectively, for the crystals of 0.1 %-14 mm and 0.25 %-12 mm. The calculations show both wavelengths lasing at 1,064.5 and 1,085.5 nm can possess the same threshold when reflectivity of the output coupler at 1,064.5 nm is less than 87.5 % and, at this condition, the reflectivity of the output coupler at 1,085.5 nm increases nearly linearly with that of 1,064.5 nm.     

Flow Injection Kinetic Spectrophotometric Determination of Cerium Based on the Decolorization Reaction Between Arsenazo III and Cerium (IV)

ABSTRACT

Trace amounts of cerium were analyzed by flow injection kinetic spectrophotometry, based on the decolorization reaction between arsenazo III and Ce(IV) in sulfuric acid medium at room temperature. The absorbance difference (ΔA) of decolorization was linear with the concentration of Ce(IV). The flow injection technique was used to precisely control the timing. Under the optimum conditions, the determination of Ce(IV) in the range 0.0–8.0 µg mL^?1 with a correlation coefficient (r) of 0.9982, the regression equation was ΔA = 0.0014 + 0.0406c (µg mL^?1). The detection limit (3σ) of 0.2 µg mL^?1 was achieved at a sampling frequency of 60 h^?1. The proposed method was applied to the analyses of Ce in soil successfully.     

Manifestation of intramolecular hydrogen bonds in the IR spectra of bioactive aminophenols

The intermolecular interactions in solutions of aminophenols in CCl₄ are studied by the methods of IR Fourier spectroscopy. If the hydroxyl groups of aminophenol molecules occupy the ortho positions with respect to the amino groups of the molecules, the hydroxyl and amino groups are involved in intramolecular interactions with the formation of hydrogen bonds O-H...N and N-H...O. The introduction of two additional tert-butyl groups into the structure of the aminophenol molecule facilitates the formation of O-H...N bonds and impedes the formation of N-H...O bonds. The occurrence of the carbonyl group in the structure of aminophenols leads to the formation of intramolecular hydrogen bonds O-H...O=C. The introduction of the methyl groups into carbonyl-containing aminophenols transforms the O-H...O=C bond into the hydrogen bond N-H...O=C.