A nuclear magnetic resonance study of molecular motion in solid diethylamine and in diethylamine clathrate deuterate

The proton magnetic resonance second moment and spin-lattice relaxation data are reported for the two solids namely pure diethylamine and diethylamine clathrate deuterate, over the temperature range 77 K to 270 K. The results indicate that in both materials the only motion which occurs at a rate great enough to affect the N.M.R. observables is methyl group reorientation and for such motion activation energies of (2·9₀±0·02) kcal mole^-1 and (2·3₄±0·02) kcal mole^-1 are obtained for pure diethylamine, and the deuterate, respectively. The strength of the dipolar interaction in the deuterate as estimated from both the second moment and the maximum in the temperature dependence of nuclear relaxation rate is consistent with a carbon-proton distance of 1·10 Å and a large degree of chemical exchange of the amine protons with the deuterons of D₂O.     

Ex situ STM imaging with atomic resolution of Ni(111) electrodes passivated in sulfuric acid

Scanning tunneling microscopy has been used to study in air Ni(111) electrodes passivated in 0.05M H₂SO₄ at + 650 mV/SHE. Before passivation, the Ni(111) single crystal surface has steps along the 〈1̄10〉 directions with terraces having a width of a few hundred nanometers. After passivation, a mosaic structure is formed with crystallites of 2 to 3 nm in size and strip-like features extended mainly along the [12̄1] direction whose width ranges from 2 to 3 nm and which appear to be locally tilted from 5 to 13°. Atomic resolution imaging has been achieved on both of these features. It reveals a corrugated lattice whose parameters are 0.30 ± 0.02 nm and 117 ± 3° in agreement with those of NiO(111). The crystallites have smooth step edges along [1̄01] and [011̄]. The STM imaging of the passive film as well as its mosaic structure are discussed.     

A new molecular silver precursor for the preparation of thin conductive silver films

The synthesis and characterization of a new molecular silver precursor is reported. The presented complex [Ag(DioxoNic)₂]NO₃ (DioxoNic=(2,2-Dimethyl-1,3-dioxolan-4-yl)methyl nicotinate) can be obtained by the reaction of silver(I) nitrate and (2,2-Dimethyl-1,3-dioxolan-4-yl)methyl nicotinate in ethanol. The product crystallizes in the monoclinic space group P21/c (No. 14). Concentrated ethanolic solutions allow the fabrication of thin films via dip coating. Using UV-irradiation and subsequent moderate temperature treatment compact films of elemental silver can be obtained. The resulting silver films show excellent electrical properties with sheet resistances down to 0.7 Ω/sq at a film thickness of 25 nm corresponding to a specific electrical resistance of 1.75×10⁻⁸ Ωm very close to the value of bulk silver. For the potential application in optoelectronic devices, the complex was tested as an ink in a soft printing process for the preparation of patterned silver films.     

The E2 admixtures in mixed multipole lines 459.7 nm and 461.5 nm in the spectrum of Bi I

A study of the hyperfine structure of mixed M1 + E2 multipole lines 459.7 nm and 461.5 nm of Bi I are reported. The computer modelling techniques was used to obtain the predicted contour of the hyperfine structure of the lines for different values of the electric-quadrupole admixtures. By variation of free parameters describing the line shape and the electric-quadrupole admixture D, defined as the ratio of the magnetic-dipole and electric-quadrupole decay rates D=A^E2/(A^M1+A^E2), the calculated profiles were fitted into the recorded spectra. The D values of the best fits found are (3.7 ± 0.8)% for the 459.7nm line and (7.7 ± 0.4)% for the 461.5nm. Our result is compared with recent theories and other experiments.     

Synthesis and optical properties of nanocrystalline ZnO powders prepared by a direct thermal decomposition route

This paper reports the synthesis and optical properties of nanocrystalline ZnO powders with crystallite sizes of 32.5 (±1.4)–43.4 (±0.4) nm prepared by a direct thermal decomposition of zinc acetate at the temperatures of 400, 500, 600, and 700°C for 4 h. The structure of the prepared samples was studied by XRD and FTIR spectroscopy, confirming the formation of wurtzite structure. The morphology of the samples revealed by SEM was affected by the thermal decomposition temperature, causing the formations of both nanoparticles and nanorods with different size and shape in the samples. The synthesized powders exhibited the UV absorption below 400 nm (3.10 eV) with a well defined absorption peak at around 285 nm (4.35 eV). The estimated direct bandgaps were obtained to be 3.19, 3.16, 3.14, and 3.13 eV for the ZnO samples thermally decomposed at 400, 500, 600, and 700°C, respectively. All the samples exhibited room-temperature photoluminescence (PL) showing a strong UV emission band at ∼395 nm (3.14 eV), a weak blue band at ∼420 nm (2.95 eV), a blue–green band at ∼485 nm (2.56 eV), and a very weak green band at ∼529 nm (2.35 eV). The mechanisms responsible for photoluminescence of the samples are discussed.     

Spectrophotometric Determination of Pyrithioxin in Pharmaceutical Preparations

Rapid direct and induced difference spectrophotometric methods for determination of pyrithioxin in single dosage forms (tablets and syrups) are reported. The direct methods depend upon measurement of the absorbance of pyrithioxin in different media at λ_max i-e at 296 nm in 0.1 M hydrochloric acid, at 328 nm in citric acid-phosphate buffer of pH 7 and at 314 nm in 0.1 M sodium hydroxide. The mean percentage recovery of the authentic samples were 100.55±0.43, 101.21±0.58 and 100.29±0.64 respectively (P=0.05). The absorbance difference methods are based upon either measurement of the difference between the acid and the alkaline solutions i-e. Δ A (Alk-Acid) at 318 nm with an accuracy of 100.72±0.88 or the absorbance difference between the acid and neutral solutions i-e Δ A (pH 7-acid) at 328 nm with an accuracy of 100.31±0.68.     

Derivative Spectrophotometric and Colorbmetric Methods for the Determination of Guanoxan Sulphate in Tablets,Urine, and Serum.

Three simple and rapid methods for the determination of guanoxan sulphate in tablets, urine and serum are presented. The first method is based on the direct measurement of the first (¹D) and second (²D) (peak-trough) derivative values at 274–250 nm and 276–260 urn respectively. The other two methods depend on the formation of a charge- transfer chromogen with either tetracyanoethylene (TCNE) and 7,7,8,8- tetracyanoquinodimethane (TCNQ). The absorbance of the color developed at 416 and 840 nm respectively. The first and second derivative (¹D & ²D) values for the charge- transfer products were also measured. The methods were proved to be accurate and reproducible as indicated by relative standard deviation of less than 2%. The proposed methods have been applied to the determination of guanoxan sulphate in tablets, and spiked human urine and serum.     

Association of riboflavin,caffeine, and sodium salicylate in aqueous solution

We have used UV and visible spectrophotometry to study self-association of aromatic riboflavin molecules (RFN, vitamin B₂, 7,8-dimethyl-10-N-(1′-D-ribityl)isoalloxazine) in aqueous solution (pH 6.86) at T = 298 K, using a dimer model. We have determined the equilibrium dimerization constant for riboflavin, K_dB = 125 ± 40 M⁻¹. We have studied heteroassociation in the system of molecules of 7,8-dimethyl-10-ribitylisoalloxazine with 1,3,7-trimethylxanthine (caffeine) and sodium salicylate (NAS) in aqueous solution (pH 6.86; T = 298 K). We have determined the heteroassociation constants for RFN-NAS and RFN-caffeine molecules in the absence and in the presence of urea in solutions using a modified Benesi-Hildebrand equation: 25 ± 4, 17 ± 3, and 74 ± 11, 53 ± 7 M⁻¹ respectively. We have determined the dimerization constants for NAS (2.7 ± 0.5 M⁻¹) and caffeine (17.0 ± 1.5 M⁻¹). We conclude that heteroassociation of the aromatic molecules leads to a lower effective riboflavin concentration in solution, and the presence of urea in mixed solutions leads to an decrease in the complexation constants for the RFN-NAS and RFN-caffeine systems. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 188–194, March–April, 2007.     

In Situ Spectrodensitometric Determination of Methyl and Propyl Parabens,Benzoic and Sorbic Acids in Bulk Powder,Foods, and Pharmaceutical Formulations

ATLC spectrodensitometric procedure was developed for the determination of methyl paraben, propyl paraben, sorbic acid and benzoic acid as bulk powders or in pharmaceutical dosage forms and foods. The procedure was used for the determination of the two parabens singly or together and also was used for the determination of benzoic and sorbic acids singly because they were found singly in some commercial food and pharmaceutical products. The cited compounds were separated on silica gel with fluorescent indicator in systems, acetone-ethanol-aqueous ammonia 28%-ethyl acetate (84:3:9:9) for the determination of benzoic and sorbic acids and n-hexane-ethyl acetate-acetic acid (80:5:20) for the determination of the two parabens. Absorbance measurement (detection of reflectance) of separated compounds was carried out in situ, at 254 nm for the two parabens, sorbic acid, and at 228 nm for benzoic acid using multilevel calibration curves in the concentration ranges of 0.2—2.5 μg/spot, 0.5—3 μg/spot, and 2.5—12.5 μg/spot for sorbic acid, the two parabens, and benzoic acid, respectively. The results were evaluated by linear regression analysis. The mean % accuracies were found to be, mean ±C.V.(%), 99.65 ±0.963, 99.45±1.02, 99.60±0.825 and 99.34±0.969 for benzoic acid, sorbic acid, methyl paraben and propyl paraben in bulk powders, respectively. While in case of benzoic and sorbic acids in foods the mean % accuracies were found to be: 97.72±1.231 and 98.81±1.296, respectively. The mean % accuracies of methyl paraben, propyl paraben, sorbic acid in pharmaceutical dosage forms were found to be: 98.19±0.874, 97.830±0.799 and 98.36±0.572, respectively.     

Ultrasonic preparation and nanosheets supported binary metal oxide nanocomposite for the effective application towards the electrochemical sensor

Binary metal oxides (La₂O₃@SnO₂) decorated reduced graphene oxide nanocomposite was synthesized by ultrasound process in an environmentally benign solvent with a working frequency of 25 and 40 kHz (6.5 l200 H, Dakshin, India and maximum input power 210 W). Further, to enhance the electrocatalytic activity, the reduced graphene oxide (rGO) was prepared from graphene oxide by ultrasonication method. As prepared La₂O₃@SnO₂/rGO was scrutinized using XRD, TEM, EDX and quantitative test for the structural and morphology properties. As modified La₂O₃@SnO₂/rGO nanocomposite exhibits better electrochemical activity towards the oxidation of methyl nicotinate with higher anodic current compared to other modified and unmodified electrode for the detection of methyl nicotinate with larger linear range (0.035–522.9 µM) and lower limit of detection (0.0197 µM). In addition, the practical feasibility of the sensor was inspected with biological samples, reveals the acceptable recovery of the sensor in real samples.     

Differential Raman cross section of dimethyl sulfide

Biogenic sulfur compounds such as dimethyl sulfide (DMS) are important contributors to the global carbon cycle. The differential Raman cross section of DMS relative to the nitrogen fundamental, σ_DMS, has been measured at several excitation wavelengths in order to assess the applicability of Raman spectroscopy for the direct quantitative measurement of this compound. At 488 nm, σ_DMS for the ν₆ carbon–sulfur stretching mode was found to be 4.9 ± 1.6, while for the ν₂ carbon–hydrogen stretching mode it was 2.8 ± 0.9. Using, KrF laser excitation, values for σ_DMS could be measured simultaneously at two excitation wavelengths, 248.32 and 248.69 nm. The average values of σ_DMS for 248‐nm excitation based on measurements at these two excitation wavelengths were 3.5 ± 1.4 for the carbon–sulfur stretching mode and 4.6 ± 0.6 for the carbon–hydrogen stretching mode. The results indicate that no significant resonance enhancement of σ_DMS for either mode occurs, although they show some slight enhancement of the cross section for the ν₂ band (C H stretching mode). It was concluded that the measured values of σ_DMS are high enough to allow the quantitative detection of DMS at the millimolar level. Copyright © 2010 John Wiley & Sons, Ltd.     

Clinical Experience with Bausch & Lomb Technolas-217 Excimer Laser

We retrospectively followed up 177 eyes of 90 myopic patients who had received laser in situ keratomileusis (LASIK) using Bausch & Lomb Technolas-217 laser. All patients underwent comprehensive preoperative ophthalmologic examinations. Results were analyzed from examinations performed at 1 week, 1, 3 and 6 months intervals after surgery. The preoperative mean spherical equivalent refraction was ?6.19 D. The 6-month follow-up rate was 86%. The mean postoperative spherical equivalent refraction was ?0.28 D. Thirty-two percent of eyes achieved 1.5 or better uncorrected visual acuity (UCVA), 86% of eyes achieved 1.2 or better UCVA and 98% achieved 1.0 or better UCVA. The safety, efficacy, predictability and the visual results were proved to be excellent     

Optical parameters measurement for diagnostic and photodynamic therapy of human cervical adenocarcinoma (HeLa) cell line

The purpose of this study was to investigate the optical properties, absorption coefficient (μ _a ) scattering coefficient (μ _s ) and refractive indices, (n) of HeLa cell line in a suspension of 2% minimum essential medium (MEM) at two different (632.8 and 532.0 nm) wave lengths of laser light. Optical properties were determined with Kubelka Munk Model (KMM) and refractive index measurement was made through minimum angle of deviation method (MAD). We reported μ _a = 8.643 ± 0.187 and 2.348 ± 0.249 cm⁻¹ and μ _s = 5.609 ± 0.287 and 88.166 ± 2.833 cm⁻¹ at 632.8 and 532.0 nm, respectively. Refractive index was found to be 1.332 and 1.312 at 632.8 nm and 532.0 nm, respectively. The discussed results provide a route of information for clinical diagnosis, therapeutic application and dosimetry studies in HeLa and other cell lines.     

Polarization squeezing with photonic crystal fibers

We report on the generation of polarization squeezing by employing intense, ultrashort light pulses in a single pass method in photonic crystal fibers. We investigated the squeezing behavior near the zero-dispersion wavelength and in the anomalous dispersion regime by using two distinct fibers. We observed a maximal squeezing at 810 nm of −3.3 ± 0.3 dB with an excess noise of +16.8 ± 0.3 dB in the anomalous regime. Correcting for linear and interference losses between the polarization modes, this corresponds to −6 ± 1 dB. The ratio of squeezing to excess noise indicates the creation of a much purer state; this ratio indeed lies an order of magnitude below those squeezing experiments that exploit traditional fibers [1]. We attribute this increased state of purity to increased effective nonlinearity and to the reduction of scattering on acoustic modes in the fiber. Original Text ? Astro, Ltd., 2007.     

Size-tuneable synthesis of nickel nanoparticles

A facile method is described for synthesising nickel nanoparticles via the thermal decomposition of an organometallic precursor in the presence of excess n-trioctylphosphine as a capping ligand. For the first time, alkylamines with different chain lengths were employed as size-limiting agents in this synthesis. A direct correlation is demonstrated between the size of the alkylamine ligands used and the mean diameter of the nickel nanoparticles obtained. The use of bulky oleylamine as a size-limiting agent over a reaction period of 30 min led to the growth of nickel nanoparticles with a mean diameter of 2.8 ± 0.9 nm. The employment of less bulky N,N-dimethylhexadecylamine groups led to the growth of nickel nanoparticles with a mean diameter of 4.4 ± 0.9 nm. By increasing the reaction time from 30 to 240 min, while employing oleylamine as the size-limiting agent, the mean diameter of the nickel nanoparticles was increased from 2.8 ± 0.9 to 5.1 ± 0.7 nm. Decreasing the amount of capping ligand present in the reaction system allowed further growth of the nickel nanoparticles to 17.8 ± 1.3 nm. The size, structure and morphology of the nanoparticles synthesised were characterised by transmission electron microscopy and powder X-ray diffraction; while magnetic measurements indicated that the particles were superparamagnetic in nature.     

Adsorption of gold on low index planes of rhenium

On atomically rough areas of a thermally cleaned rhenium field emitter, adsorbed gold behaves like it does on tungsten. The average work function $\text{}\text{?}$gf increases at low average gold coverage $\text{}\text{?}$gq due to formation of gold-rhenium dipoles, and at high coverage a structural transformation in the gold layer leads to a $\text{}\text{?}$gq-independent work function. Broadly similar behaviour is found for gold on the low-index planes of tungsten, but on low-index rhenium planes gold behaves rather differently. When thermally cleaned at > 2200 K and annealed below 800 K, the work function, φ(clean), of (101&#x0304;1&#x0304;) takes one of two values 5.25 ± 0.04 eV, and 5.36 ± 0.04 eV, which are tentatively attributed to the two possible structures of this plane. Similar behaviour is expected and observed for (101&#x0304;0),but the values taken by φ(clean) are not well defined. Both forms of (101&#x0304;1&#x0304;) are thought to undergo reconstruction above 800 K forming a single structure with φ(clean) = 5.55 ± 0.03 eV. (112&#x0304;0) and (112&#x0304;2&#x0304;) each have only one possible structure, and in keeping with this, φ(clean) has a single well-defined value for each plane. The flatness of (101&#x0304;1&#x0304;) and (101&#x0304;0) leads to field reduction at their centres which produces an increase in their measured work functions by up to 10%. The initial increase in φ produced by gold condensed at 78 K and spread at low equilibration temperatures T_s on (112&#x0304;2&#x0304;), (101&#x0304;1&#x0304;) and (112&#x0304;0) is attributed to gold-rhenium dipoles, which, on the latter two planes approximate to the Topping model, giving dipoles characterised by μ₀(1011) = 0.1 × 10^?30 C-m with α = 10 ų and μ₀(112&#x0304;0) = 0.32 × 10^?30 C-m with α = 22 ų, where μ₀ is the zero-coverage dipole moment and α its polarizability. Failure of the Topping model on (112&#x0304;2&#x0304;) is attributed to its atomically rough structure. No dipole effect is seen on (101&#x0304;0). Energy spectroscopy of electrons field emitted at (202&#x0304;1&#x0304;) and (101&#x0304;1&#x0304;) demonstrates the non-free character of electrons in rhenium, while the small effect of adsorbed gold strengthens the belief that gold is bound through a greatly broadened 6s level centred 5.6 eV below the Fermi level and the dipolar nature of the bond supports this model. At higher values of T_s and $\text{}\text{?}$gq gold appears to form states which are well-characterised by a coverage-independent work function. (101&#x0304;0), (101&#x0304;1&#x0304;) and (112&#x0304;0) each form two such states, one in the range 2 < $\text{}\text{?}$gq < 4 (state 1), and the second at $\text{}\text{?}$gq > 4 (state 2). The atomic radii of gold and rhenium are thought to be sufficiently similar to allow the possibility that state 1 is a replication of the Re plane structure by gold. The high work function and thermal stability of state 2, taken together with the observed temperature dependence of the transformation of state 1 to state 2, encourages the belief that state 2 results from atomic rearrangement of state 1 into a close-packed Au(111) structure. State 2 also forms on (112&#x0304;2&#x0304;) and the absence of state 1 on this plane suggests some surface alloying at coverages below 4 $\text{}\text{?}$gq.     

基于二维结构薄膜的偏振选择相位光栅的研究

利用二维结构薄膜构建了具有偏振选择特性的新型相位光栅,借助严格耦合波分析(RCWA)方法计算了光栅各级衍射强度随入射光波长及入射角的变化,发现在垂直入射情况下,波长600—640 nm范围内,相位光栅对横向电学(TE)模主要产生0级衍射,而对横向磁学(TM)模产生±1级衍射,在波长633nm处,0级衍射光的偏振消光比为109.8,±1级衍射光的偏振消光比为334.6.利用时域有限差分方法对这种相位光栅的偏振分束现象进行了模拟,偏振分离角在玻璃基板内可以达到10°左右,最后模拟了入射角为23°时光栅对不同偏     

Gold nanorods surface modified with poly(acrylic acid) as a template for the synthesis of metallic nanoparticles

Poly(acrylic acid) (PAA) surface-modified gold nanorods, contained in deionized ultra filtered (DIUF) water, served as templates for the formation of gold (Au), palladium (Pd), and platinum (Pt) nanoparticles upon reduction with NaBH₄. This provided nanoparticles with respective diameters of 7.0 ± 0.7, 4.1 ± 0.4, and 5.1 ± 0.5 nm. Varying amounts of Pt metal salt were used in EG, which acts as both a solvent and a reducing agent, ranging from 0.1, 0.2, and 1.0 mg/mL, to provide control over nanoparticle diameters of 2.0 ± 0.5 nm, to 4.0 ± 0.5 nm, and 6.2 ± 1.9 nm, respectively. Nanoparticle diameter was also controlled in DIUF water by varying the amount of Pt metal salt from 0.1, 0.2, and 1.0 mg/mL, producing Pt particle diameters, respectively, increasing from 2.7 ± 0.3 nm to 4.1 ± 0.5 nm, and 6.0 ± 0.6 nm.     

Conventional and First Derivative Synchronous Fluorometric Determination of Ethamsylate in Pharmaceutical Preparations and Biological Fluids. Application to Stability Studies

Two simple, accurate and highly sensitive spectrofluorometric methods were developed for the determination of ethamsylate (ETM). Method I is based on measuring the native fluorescence of ethamsylate in water at 354 nm after excitation at 302 nm. The calibration plot was rectilinear over the range of 0.05–1 μg/mL for ETM with limits of detection and quantitation of 7.9 and 26 ng/mL, respectively. Method II involved synchronous and first derivative synchronous fluorometric methods for the simultaneous determination of ethamsylate (ETM) and hydroquinone (HQ) which is considered as an impurity and/or acidic degradation product. The synchronous fluorescence of both the drug and its impurity were measured in methanol at Δ λ of 40 nm. The peak amplitudes (¹D) were estimated at 293.85 or 334.17 nm for ETM and at 309.05 nm for HQ. Good linearity was obtained for ETM over the ranges 0.1–1.4 μg/mL and 0.1–1.0 μg/mL at 293.85 and 334.17 nm, respectively. For HQ, the calibration plot was rectilinear over the range of 0.01–0.14 μg/mL at 309.05 nm. Limits of detection were 20, 2.01 ng/mL and limits of quantitation were 60, 6.7 ng/mL for ETM and HQ by method II, respectively. Both methods were successfully applied to commercial ampoules and tablets. The results were in good agreement with those obtained by the reference method. Method I was utilized to study the stability of ETM and its degradation kinetics using peroxide. The apparent first-order rate constant, half-life times and activation energy of the degradation process were calculated. Method I was further extended to the in-vitro and in-vivo determination of ETM in spiked and real plasma samples. The mean% recoveries were 99.57 ± 3.85 and 89.39 ± 5.93 for spiked and real human plasma, respectively.     

Luminescence and decay times of CsI:In+

Luminescence spectra of single crystals of CsI:In⁺ excited in the A(304 nm), B(288 nm), C(268 nm) and D(257 nm) absorption bands have been studied in the temperature range 4.2–300 K. Excitation in the A band at 4.2 K gives rise to the principal emission at 2.22 eV accompanied by a partly-overlapping weak band at 2.49 eV. An additional emission band at about 2.96 eV is observed on excitation in the B, C or D bands. Yet another emission band located at 2.67 eV is excited only in the D band. The relative intensities of the bands are very sensitive to excitation wavelength as well as to temperature. The origin of all these bands is assigned in terms of a model for the relaxed excited states (RES). All the luminescence spectra were resolved into an appropriate number of skew-Gaussian components. Moments analysis leads to a value of (1.35 ± 0.02) × 10¹³ rad s^-1 for the effective frequency (ω_eff) of lattice vibrations coupled to the RES. At the lowest temperature, the radiative decay times of each of the intracenter emission bands (2.22, 2.49 and 2.96 eV) show a slow decay ( ～ 10–100 μs) and a fast decay ( ～ 10–100 ns). The 2.96 eV band, which is assigned to an emission process which is the inverse of the D-band absorption, exhibits a single decay mode ( ～ 10 μs). The intrinsic radiative decay rates (k₁, k₂), the one-phonon transition rate (K) and the second-order spin-orbit splitting (D) for the RES responsible for the principal emission are: k₁ = (6.0±-0.3)×10³ s^-1, k₂ = (1.33±-0.06)×10⁵ s^-1, K = (2.4±-0.4)×10⁷ s^-1 and D = (13.8±-0.5) cm^-1.