Cluster-assistant generation of multiply charged atomic ions in nanosecond laser ionization of seeded methyl iodide beam

The photoionization of methyl iodide beam seeded in argon and helium is studied by time-of-flight mass spectrometry using a 25 ns, 532 nm Nd-YAG laser with intensities in the range of 2 × 10¹⁰–2 × 10¹¹ W/cm². Multiply charged ions of I^q+ (q = 2–3) and C²⁺ with tens of eV kinetic energies have been observed when laser interacts with the middle part of the pulsed molecular beam, whose peak profiles are independent on the laser polarization directions. Strong evidences show that these ions are coming from the Coulomb explosion of multiply charged CH₃I clusters, and laser induced inverse bremsstrahlung absorption of caged electrons plays a key role in the formation of multiply charged ions.     

Influence of wavelength,irradiance, and the buffer gas pressure on high irradiance laser ablation and ionization source coupled with an orthogonal Time of Flight Mass Spectrometer

Influence of laser wavelength, laser irradiance and the buffer gas pressure were studied in high irradiance laser ablation and ionization source coupled with an orthogonal time-of-flight mass spectrometer. Collisional cooling effects of energetic plasma ions were proved to vary significantly with the elemental mass number. Effective dissociation of interferential polyatomic ions in the ion source, resulting from collision and from high laser irradiance, was verified. Investigation of relative sensitivity coefficients (RSC) of different elements performed on a steel standard GBW01396, which was ablated at 1064 nm, 532 nm, 355 nm, and 266 nm, has demonstrated that the thermal ablation mechanism could play a critical role with the first three wavelengths, while 266 nm induces non-thermal ablation principally. Experimental results also indicated that there is no evident discrepancy for most metal elements on RSCs and LODs among four wavelengths at high irradiance, except that high boiling point elements like Nb, Mo, and W have higher RSCs at higher irradiance regions of 1064 nm, 532 nm, and 355 nm due to thermal ablation. A geological standard and a garnet stone were also used in the experiment subsequently, and their RSCs and LODs for metal elements show nonsignificant dependence on wavelength at designated irradiances. All results reveal that relatively uniform sensitivity can be achieved at any wavelength for metal elements in the solids used in our experiments at an appropriate irradiance for the low pressure high irradiance laser ablation and ionization source.     

Experimental determination of laser induced breakdown thresholds of metals under nanosecond Q-switched laser operation

Laser-induced breakdown thresholds for several pure metals were determined using a nanosecond laser. A Q-switched pulsed Nd:YAG laser operating at infrared (1064 nm), visible (532 nm) and ultraviolet (266 nm) wavelengths has been used. The plasma was generated by focusing the Nd:YAG laser on the target in air at atmospheric pressure. The dispersed plasma light was detected using a two-dimensional intensified charge-coupled device (CCD) detector. The studied elements were chosen according to their different thermal and physical properties, particularly boiling point, melting point and thermal conductivity. The effect of wavelength on the plasma threshold has been discussed. Laser fluence thresholds in the ultraviolet were larger than those obtained using visible and infrared radiation, while the energy threshold is larger using infrared radiation. Correlations between the plasma threshold of metal targets and the melting point and boiling point at 266, 532 and 1064 nm have been established. The results indicate that thermal effects have an important influence on the ablation behavior of metals at the three wavelengths used.     

Carbon ion irradiation induced surface modification of polypropylene

Polypropylene was irradiated with ¹²C ions of 3.6 and 5.4 MeV energies in the fluence range of 5×10¹³–5×10¹⁴ ions/cm² using 3 MV tandem accelerator. Ion penetration was limited to a few microns and surface modifications were investigated by scanning electron microscopy. At the lowest ion fluence only blister formation of various sizes (1–6 μm) were observed, but at higher fluence (1×10¹⁴ ions/cm²) a three-dimensional network structure was found to form. A gradual degradation in the network structure was observed with further increase in the ion fluence. The dose dependence of the changes on surface morphology of polypropylene is discussed.     

Photoinduced electron transfer in crystal violet (CV)–bovine serum albumin (BSA) system: evaluation of reaction paths and radical intermediates

Photoinduced electron transfer (PET) from excited probes attached to proteins is of considerable current interest. Photochemical processes following 532 nm excitation of triphenyl methane dye, crystal violet (CV⁺) bound to a protein, bovine serum albumin (BSA), have been investigated in picosecond (ps) to microseconds (μs) time scales by flash photolysis technique. The excited singlet state lifetime of CV⁺ is found to be increased to 130 ps as compared to 1–5 ps for the unbound dye in low viscosity solvents. From flash photolysis studies in microsecond region, transient absorption in the region 650 nm is observed which is attributed to the dication radical CV√²⁺ formed by electron transfer from ³CV^+* to BSA, contrary to electron transfer from BSA to the excited dye as proposed in a recent report. Supporting spectral evidence for the electron transfer from ³CV^+* to BSA is obtained from pulse radiolysis studies.     

Excited species in the FBX dosimeter system

In the FBX dosimeter solution, the excitation of xylenol orange (XO) produces maximum emission at 550–575 nm both at room and liquid nitrogen temperatures (about 85%) having a lifetime of 0.20–0.36 ns. In addition, at room temperature there is an emission at 350 nm for the excitation at 260 nm (about 15%) having a longer lifetime of 3.71–4.01 ns. Benzoic acid (BA) has excitation at 284–295 nm and emission at 320–365 nm having a lifetime of 1.38 ns. In an aqueous solution containing 5×10⁻³ mol dm⁻³ BA, 2×10⁻⁴ mol dm⁻³ XO and 0.04 mol dm⁻³ H₂SO₄ there is no XO emission at 550 nm due to UV absorption at 260 nm by BA. In this solution, 2 emissions are observed near 350–360 nm, having lifetimes of 1.25 ns (89%) and 2.86 ns (11%). The wavelengths for the emission of XO and absorption of ferric-XO complex are nearly the same. Excited XO produces oxidation of ferrous ions and BA increases the chain length.     

Comparison of the effects of visible femtosecond laser pulses and continuous wave laser radiation of low average intensity on the clonogenicity of Escherichia coli.

To evaluate the contribution of local pulsed heating of light-absorbing microregions to biochemical activity, irradiation of Escherichia coli was carried out using femtosecond laser pulses (λ = 620 nm, τ_p=3 × 10⁻¹³ s, f_p = 0.5 Hz, E_p = 1.1 × 10⁻³J cm⁻², I_av = 5.5 × 10⁻⁴ W cm⁻², I_p = 10⁹ W cm⁻²) and continuous wave (CW) laser radiation (λ = 632.8 nm, I = 1.3 W cm⁻²). The irradiation dose required to produce a similar biological effect (a 160%–190% increase in the clonogenic activity of the irradiated cells compared with the non-irradiated controls) is a factor of about 10³ lower for pulsed radiation than for CW radiation (3.3 × 10⁻¹ and 7.8 × 10² J cm⁻² respectively). The minimum size of the microregions transiently heated on irradiation with femtosecond laser pulses is estimated to be about 10 Å, which corresponds to the size of the chromophores of hypothetical primary photoacceptors—respiratory chain components.     

Role of laser pre-pulse wavelength and inter-pulse delay on signal enhancement in collinear double-pulse laser-induced breakdown spectroscopy

Dual-pulse (DP) laser-induced breakdown spectroscopy (LIBS) provides significant improvement in signal intensity as compared to conventional single-pulse LIBS. We investigated collinear DPLIBS experimental performance using various laser wavelength combinations employing 1064 nm, 532 nm, and 266 nm Nd:YAG lasers. In particular, the role of the pre-pulse laser wavelength, inter-pulse delay times, and energies of the reheating pulses on LIBS sensitivity improvements is studied. Wavelengths of 1064 nm, 532 nm, and 266 nm pulses were used for generating pre-pulse plasma while 1064 nm pulse was used for reheating the pre-formed plasma generated by the pre-pulse. Significant emission intensity enhancement is noticed for all reheated plasma regardless of the pre-pulse excitation beam wavelength compared to single pulse LIBS. A dual peak in signal enhancement was observed for different inter-pulse delays, especially for 1064:1064 nm combinations, which is explained based on temperature measurement and shockwave expansion phenomenon. Our results also show that 266 nm:1064 nm combination provided maximum absolute signal intensity as compared to 1064 nm:1064 nm or 532 nm:1064 nm.     

Evidence for two light-induced metastable states in Cl3[Ru(NH3)5NO]H2O

Differential Scanning Calorimetry measurements on irradiated Cl₃[Ru(NH₃)₅NO]H₂O reveal the existence of two light-induced long-lived metastable states SI, SII. Irradiation with light in the spectral range 400–500 nm leads to the excitation of SI. For the first time we report experimental evidence for the state SII in this compound, which can be excited by transferring SI into SII with irradiation of light in the spectral range 1000–1200 nm. The excitation and transfer of the metastable states is described and the exponential decays are evaluated according to Arrhenius' law yielding activation energies of E_A(SI)=0.73(3) eV, E_A(SII)=0.66(3) eV and frequency factors of Z(SI)=1 × 10¹² s⁻¹, Z(SII) = 5 × 10¹² s⁻¹.     

Studies on adducts of rhodium(II) tetraacetate and rhodium(II) tetratrifluoroacetate with some amines in CDCl3 solution using H, C and N NMR

¹H, ¹³C and ¹⁵N NMR spectroscopy has been applied for investigation of amine adducts with rhodium(II) tetraacetate dimer and rhodium(II) tetratrifluoroacetate dimer in CDCl₃ solution. Subsequent formation of two adducts, 1:1 and 2:1, was proved by NMR and VIS titration experiments, and by NMR measurements at reduced temperatures, from 233 to 273 K. The adduct formation shift, defined as Δδ=δ_adduct−δ_ligand and characterizing complexation reaction, varies from ca. 0 to +1.6 ppm for ¹H, from ca. −10 to +6 ppm for ¹³C and from −4.4 to −39 ppm for ¹⁵N NMR. Formation of N–Rh bond slows the inversiof on the nitrogen atom and generates, in the case of N-methyl-(1-phenylethyl)-amine, a nitrogenous chiral center in the molecule. VIS spectra of amine-dirhodium salt mixture contain two bands in the 532–597 nm spectral range, assigned to 1:1- and 2:1-adducts.     

The second and third order non-linear optical properties of liquid crystalline polymers

The second and third order non-linear optical susceptibilities of several donoracceptor substituted side chain polymers, some of which exhibit mesophases, will be reported. The susceptibilities were measured by harmonic generation from thin films, typically 0·5 μm thick, at a fundamental wavelength of 1064 nm and 1579 nm. For second harmonic generation, the spin coated films were contact poled on a glass substrate with an interdigited electrode pattern. Typical values obtained were χ⁽²⁾₃₁ = 1 × 10^-9 esu and χ⁽²⁾₃₃ = 3 × 10^-9 esu, the largest value was χ⁽²⁾₃₃ = 6·3 × 10^-9 esu. The difficulty in deriving reliable second order structure-property relations because of the large effect which the contact poling process has on the non-linear optical susceptibility of the films will be highlighted. The highest χ⁽³⁾ value of 5·8 × 10^-12 esu obtained from an amorphous film of a polymer with an asymmetrically substituted azo side group is comparable with the susceptibility of more typical third order non-linear materials such as the main chain polymers polyphenylacetylene and poly-p-phenylenebenzobisthiazole.     

Calorimetric comparison of the interactions between salivary proteins and Streptococcus mutans with and without antigen I/II

Antigen I/II can be found on streptococcal cell surfaces and is involved in their interaction with salivary proteins. In this paper, we determine the adsorption enthalpies of salivary proteins to Streptococcus mutans LT11 and S. mutans IB03987 with and without antigen I/II, respectively, using isothermal titration calorimetry. In addition, protein adsorption to the cell surfaces was determined spectrophotometrically. S. mutans LT11 with antigen I/II, yielded a much higher, exothermic adsorption enthalpy at pH 6.8 (ranging from −2073 × 10⁻⁹ to −31707 × 10⁻⁹ μJ per bacterium) when mixed with saliva than did S. mutans IB03987 (−165 × 10⁻⁹ to −1107 × 10⁻⁹ μJ per bacterium) at all bacterial concentrations studied (5 × 10⁹, 5 × 10⁸, and 5 × 10⁷ ml⁻¹), largest effects per bacterium being observed for the lowest concentration. However, the enthalpy of salivary protein adsorption to S. mutans LT11 became smaller at pH 5.8. Adsorption isotherms for the S. mutans LT11 showed considerable protein adsorption at pH 6.8 (1.2–2.1 mg/m²), that decreased only slightly at pH 5.8 (1.1–1.6 mg/m²), with the largest amount adsorbed at the lowest bacterial concentration. This suggests that the protein(s) in the saliva with the strongest affinity for antigen I/II is (are) readily depleted from saliva. In conclusion, antigen I/II surface proteins on S. mutans play a determinant role in adsorption of salivary proteins through the creation of enthalpically favorable adsorption sites.     

Spectral characterization of a novel near-infrared cyanine dye: a study of its complexation with metal ions

The spectral features of the near-infrared (NIR) dye TG-170 in different solutions and its complexation with several metal ions were investigated. The absorbance maxima of the dye are at λ=819, 805, and 791 nm in dimethyl sulfoxide (DMSO), methanol, and a buffer of pH 5.9, respectively. These values match the output of a commercially available laser diode (780 nm), thus making use of such a source practical for excitation. The emission wavelengths of the dye are at λ_em =822, 812, and 803 nm in DMSO, methanol, and the buffer, respectively. The molar absorptivity and fluorescence quantum yield increase accordingly. The addition of either an Al(III) ion or Be(II) ion resulted in fluorescence quenching of the dye. The Stern–Volmer quenching constant, K_SV, was calculated from the Stern–Volmer plot to be K_SV=3.11×10⁵ M⁻¹ for the Al(III) ion and K_SV=1.17×10⁶ M⁻¹ for the Be(II) ion. The molar ratio of the metal to the dye was established to be 1:1 for both metal ions. The stability constant, K_S, of the metal–dye complex was calculated to be 4.37×10⁴ M⁻¹ for the Al–dye complex and 1.94×10⁶ M⁻¹ for the Be–dye complex.     

A precise measurement of the Cotton–Mouton effect in neon

In this Letter, we report a novel measurement of the magnetically induced birefringence (Cotton–Mouton effect) in neon. Using a highly sensitive apparatus we were able to precisely measure the specific birefringence value of Δn_u = (5.9 ± 0.2) × 10⁻¹⁶ at the wavelength of 1064 nm (for B = 1 T and atmospheric pressure) and T ≈ 290 K. The results reported here are in agreement with theory, while the only previous precise measurement differs significantly.     

Ultrafast photodissociation dynamics of HMX and RDX from their excited electronic states via femtosecond laser pump–probe techniques

Femtosecond laser pump–probe techniques are employed to investigate the mechanisms and dynamics of the photodissociation of HMX and RDX from their excited electronic states at three wavelengths (230 nm, 228 nm, and 226 nm). The only observed product is the NO molecule. Parent HMX and RDX ions are not observed. The NO molecule has a resonant A²Σ ← X²Π (0, 0) transition at 226 nm and off-resonance two-photon absorption at 228 nm and 230 nm. Pump–probe transients of the NO product at both off-resonance and resonance absorption wavelengths indicate the decomposition dynamics of HMX and RDX falls into the timescale of our laser pulse duration (180 fs).     

Gamma rays produced by inverse Compton scattering in the Super-ACO storage ring free electron laser

The inverse Compton scattering between positron bunches and the free electron laser (FEL) of the Super-ACO storage ring generates a collimated and tunable gamma-ray beam. The use of the FEL instead of an external conventional laser, automatically provides the transverse alignment and synchronisation of the electron and optical beams. The Super-ACO FEL is operated in the 300–430 nm range at 800 MeV with a high repetition rate (8 MHz) and an average transmitted power of 300 mW at 350 nm. High energy gamma-rays of 35 MeV are produced with a rate of 1.5×10⁷ photons/s and good monochromaticity (about 10%).     

Synthesis, crystal structure and third-order non-linear optical property of heterobimetallic cluster compound [MoOICu3S3(2,2′-bipy)2]

Nest-shaped cluster [MoOICu₃S₃(2,2′-bipy)₂] (1) was synthesized by the treatment of (NH₄)₂MoS₄, CuI, (n-Bu)₄NI, and 2,2′-bipyridine (2,2′-bipy) through a solid-state reaction. It crystallizes in monoclinic space group P2₁/n, a=9.591(2) Å, b=14.820(3) Å, c=17.951(4) Å, β=91.98(2)°, V=2549.9(10) ų, and Z=4. The nest-shaped cluster was obtained for the first time with a neutral skeleton containing 2,2′-bipy ligand. The non-linear optical (NLO) property of [MoOICu₃S₃(2,2′-bipy)₂] in DMF solution was measured by using a Z-scan technique with 15 ns and 532 nm laser pulses. The cluster has large third-order NLO absorption and the third-order NLO refraction, its ₂ and n₂ values were calculated as 6.2×10⁻¹⁰ and −3.8×10⁻¹⁷ m² W⁻¹ in a 3.7×10⁻⁴ M DMF solution.     

Micellar effects on photoinduced redox reactions of Fe(bpy)2(CN)2

Excitation of solutions of Fe(bipy)₂(CN)₂ by a 266-nm laser pulse produces a hydrated electron and the oxidized complex, Fe(bipy)₂ (CN)₂⁺, in the primary photochemical step, in homogeneous aqueous solution as well as in aqueous solutions containing cetyltrimethylammonium bromide (CTAB) or sodium dodecyl sulfate (SDS) micelles. In all cases nascent hydrated electrons react with ground state Fe(bipy)₂(CN)₂ to form Fe(bipy)₂(CN)₂⁻, and comparison of the decay constants in the three media (H₂O: k = 2.8 × 10¹⁰ M⁻¹ s⁻¹; CTAB: k = 2.9 × 10¹⁰ M⁻¹ s⁻¹; SDS: k = 5.5 × 10⁹ M⁻¹ s⁻¹), shows that the reaction is essentially unaffected by CTAB micelles but is much slower in SDS solution. Similar micellar effects were found for the back reaction between e_aq⁻ and Fe(bpy)₂(CN)₂⁺. Rate constants for the scavenging of the photogenerated hydrated electrons by methyl viologen (MV²⁺) cations and NO₃⁻ anions were measured in the three systems, and the results indicate that for scavenging by MV²⁺ the rate constants are decreased in the micelle systems (k in H₂O, 8.4 × 10¹⁰; CTAB, 3.5 × 10¹⁰ and SDS, 1.58 × 10¹⁰ M⁻¹ s⁻¹), whereas for NO₃⁻ the CTAB micelle decreases while the SDS micelle enhances the scavenging compared to water solution (k in H₂O, 8.3 × 10⁹; CTAB, 7 × 10⁸; and SDS, 2.05 × 10¹⁰ M⁻¹ s⁻¹). For the comproportionation reaction between Fe(bipy)₂(CN)₂⁺ and Fe(bipy)₂(CN)₂⁻ both micelles reduce the rate (k in H₂O, 3.3 × 10¹⁰; CTAB, 2.3 × 10¹⁰; and SDS, 1.05 × 10¹⁰ M⁻¹s⁻¹), but while the reaction of Fe(bipy)₂(CN)₂⁺ with MV⁺ is increased in CTAB compared to water, it is slowed in SDS (k in H₂O, 2.4 × 10¹⁰; CTAB, 8.9 × 10¹⁰; and SDS, 1.8 × 10¹⁰ M⁻¹s⁻¹). All effects observed in these microheterogeneous systems can be uniformly interpreted in terms of Coulombic interactions between the actual reactants and the charged surface of the micelles.     

Research on radiation-induced color change of white topaz

In the present study, a method of producing sky blue topaz is studied. A 3–5 MeV scanning electron beam linear accelerator (which is currently used for processing semiconductor devices) was employed to change the color of white topaz under room-temperature conditions, together with a cooling device. A radiation-induced ion color center is formed in white topaz by an electron beam. To finish the irradiation, the total dose needs to be more than 5×10⁷–1×10⁸ Gy, the temperature of heat-treatment was between 180°C and 280°C in air conditions, after a while, a sky blue topaz was obtained.

There was a bright color and no radioactivity was formed in the sky blue topaz by this production method.     

Generation of surface energy patterns by single pulse laser interference on self-assembled monolayers

Single pulse laser interference lithography is used to structure self-assembled monolayers of thiols on gold. This structuring process is investigated by attenuated total reflection measurements, and a demixing process of a binary polymer blend is used to visualize the produced surface energy pattern. The lithography can be realized with different wavelengths (266, 532, and 1064 nm) which shows that the structuring is a thermal process. As a first demonstration of this process, structures down to 800 nm period and 300 nm width are fabricated.