Highly sensitive detection of broadband terahertz waves using aqueous salt solutions.

Water-based coherent detection of broadband terahertz (THz) wave has been recently proposed with superior performances, which can alleviate the limited detection bandwidth and high probe laser energy requirement in the solid- and air-based detection schemes, respectively. Here, we demonstrate that the water-based detection method can be extended to the aqueous salt solutions and the sensitivity can be significantly enhanced. The THz coherent detection signal intensity scales linearly with the third-order nonlinear susceptibility χ(3) or quadratically with the linear refractive index η0 of the aqueous salt solutions, while the incoherent detection signal intensity scales quadratically with χ(3) or quartically with η0, proving the underlying mechanism is the four-wave mixing. Both the coherent and incoherent detection signal intensities appear positive correlation with the solution concentration. These results imply that the liquid-based THz detection scheme could provide a new technique to measure χ(3) and further investigate the physicochemical properties in the THz band for various liquids.

Water-Based Coherent Detection of Broadband Terahertz Pulses.

Both solids and gases have been demonstrated as the materials for terahertz (THz) coherent detection. The gas-based coherent detection methods require a high-energy probe laser beam and the detection bandwidth is limited in the solid-based methods. Whether liquids can be used for THz detection and relax these problems has not yet been reported, which becomes a timely and interesting topic due to the recent observation of efficient THz wave generation in liquids. Here, we propose a THz coherent detection scheme based on liquid water. When a THz pulse and a fundamental laser beam are mixed on a free-flowing water film, a second harmonic (SH) beam is generated as the plasma is formed. Combining this THz-induced SH beam with a control SH beam, we successfully achieve the time-resolved waveform of the THz field with the frequency range of 0.1-18 THz. The required probe laser energy is as low as a few microjoules. The sensitivity of our scheme is 1 order of magnitude higher than that of the air-based method under comparable detection conditions. The scheme is sensitive to the THz polarization and the phase difference between the fundamental and control SH beams, which brings direct routes for optimization and polarization sensitive detection. Energy scaling and polarization properties of the THz-induced beam indicate that its generation can be attributed to a four-wave mixing process. This generation mechanism makes simple relationships among the probe laser, THz-induced SH, and THz field, favorable for robustness and flexibility of the detection device.

Observation of Terahertz Radiation via the Two-Color Laser Scheme with Uncommon Frequency Ratios.

In the widely studied two-color laser scheme for terahertz (THz) radiation from a gas, the frequency ratio of the two lasers is usually fixed at ω_{2}/ω_{1}=1:2. We investigate THz generation with uncommon frequency ratios. Our experiments show, for the first time, efficient THz generation with new ratios of ω_{2}/ω_{1}=1:4 and 2∶3. We observe that the THz polarization can be adjusted by rotating the longer-wavelength laser polarization and the polarization adjustment becomes inefficient by rotating the other laser polarization; the THz energy shows similar scaling laws with different frequency ratios. These observations are inconsistent with multiwave mixing theory, but support the gas-ionization or plasma-current model. This study pushes the development of the two-color scheme and provides a new dimension to explore the long-standing problem of the THz generation mechanism.

[Terahertz Spectroscopic Investigation of Substrate Materials for Biological Application in the Frequency Range of 1～15 THz].

As emerging modalities, terahertz time-domain spectroscopy and imaging have been widely applied to investigate the optical properties of different biological tissues. The substrate materials are usually needed for biological spectroscopic measurements. The ultra-broadband and facility in remote sensing of the terahertz air-biased-coherent-detection (ABCD) system mean it is a good potential tool for the spectroscopic study of biological tissues. In this paper, the optical parameters of four typical substrate materials (quartz, high-density polyethylene, teflon and paraffin) are measured using terahertz ABCD spectrometer. The absorption coefficients and refractive indices are presented in the frequency range of 1～15 THz. It is demonstrated that high-density polyethylene and paraffin are good candidates as sample substrate for broadband terahertz biological spectroscopic measurement. However, quartz and teflon which are common substrate materials in narrowband (0.1～3 THz) terahertz system can not be utilized in high terahertz frequency range because they have strong absorption above 5 THz.

[The Detection of Ultra-Broadband Terahertz Spectroscopy of InP Wafer by Using Coherent Heterodyne Time-Domain Spectrometer].

Indium Phosphide (InP) has attracted great physical interest because of its unique characteristics and is indispensable to both optical and electronic devices. However, the optical property of InP in the terahertz range (0. 110 THz) has not yet been fully characterized and systematically studied. The former researches about the properties of InP concentrated on the terahertz frequency between 0.1 and 4 THz. The terahertz optical properties of the InP in the range of 4-10 THz are still missing. It is fairly necessary to fully understand its properties in the entire terahertz range, which results in a better utilization as efficient terahertz devices. In this paper, we study the optical properties of undoped (100) InP wafer in the ultra-broad terahertz frequency range (0.5-18 THz) by using air-biased-coherent-detection (ABCD) system, enabling the coherent detection of terahertz wave in gases, which leads to a significant improvement on the dynamic range and sensitivity of the system. The advantage of this method is broad frequency bandwidth from 0.2 up to 18 THz which is only mainly limited by laser pulse duration since it uses ionized air as terahertz emitter and detector instead of using an electric optical crystal or photoconductive antenna. The terahertz pulse passing through the InP wafer is delayed regarding to the reference pulse and has much lower amplitude. In addition, the frequency spectrum amplitude of the terahertz sample signal drops to the noise floor level from 6.7 to 12.1 THz. At the same time InP wafer is opaque at the frequencies spanning from 6.7 to 12.1 THz. In the frequency regions of 0.8-6.7 and 12.1-18 THz it has relativemy low absorption coefficient. Meanwhile, the refractive index increases monotonously in the 0.8-6.7 THz region and 12.1-18 THz region. These findings will contribute to the design of InP based on nonlinear terahertz devices.

[Application of Terahertz Spectroscopy in the Detection of Chinese Medicine Processed Drugs of Rhubarb].

The changes of composition of the processed traditional Chinese medicine will affect the curative effect of drug, such as the four kinds of processed rhubarb. The characteristics data of each rhubarb was measured with terahertz spectroscopy system and analyzed with chemometrics, and the spectral data was classified according to the category of rhubarb. The substance components of anthraquinone and tannins make changes in processed rhubarb by thin layer chromatography (TLC). The correlation among the terahertz spectroscopy of processed rhubarb was in accordance with the variations of content. This means that terahertz spectroscopy is sensitive to the substance components of processed Chinese traditional medicine. It can also pave the way for the study of the structural changes of traditional Chinese medicine.

[The Study on the Far-FTIR and THz Spectra of Azitromycin Drugs with Different Physical Forms].

Far Fourier transform infrared spectroscopy (Far-FTIR) and terahertz time-domain spectroscopy (THz-TDS) were used to measure the fingerprint spectra of Azitromycin suspension, capsule, tablet and dispersible tablet under vacuum and nitrogen conditions, respectively. In the frequency range of 0.2-15 THz, highly resolved spectral features for Azitromycin suspension were measured and some minor differences were observed between domestic and exotic Azitromycin Suspension, such as linewidth broadening and additional peaks. As same time, for the domestic Azitromycin capsule, tablet and dispersible tablet, the absorption baselines in the range of 0.2-2.7 THz rise with the increase of frequency while absorption peaks become weaker due to the scattering of bigger particles and smaller amount of Azitromycin. Also, the additional peaks are caused by the absorption of filling materials. In parallel with the qualitative measurement, the THz absorption spectra for mixtures of polyethylene (PE) powders and exotic Azithomycin suspension with different concentrations were also measured. According to the linear correlation between the concentration and the absorption intensity, the concentration of effective component can be evaluated accurately. This means that THz-TDS method is suitable for the quality inspection and evaluation of the mixed Azithromycin system.

6-Nitro-1,3-benzothia-zole-2(3H)-thione.

In the title mol-ecule, C(7)H(4)N(2)O(2)S(2), the nitro group is twisted by 5.5 (1)° from the plane of the attached benzene ring. In the crystal, N-H⋯S hydrogen bonds link pairs of mol-ecules into inversion dimers, which are linked by weak C-H⋯O inter-actions into sheets parallel to (101). The crystal packing exhibits short inter-molecular S⋯O contacts of 3.054 (4) Šand π-π inter-actions of 3.588 (5) Šbetween the centroids of the five- and six-membered rings of neighbouring mol-ecules.

3-Amino-1H-1,2,4-triazole-5(4H)-thione-4,4'-bipyridine (1/1).

The title two-component mol-ecular crystal, C(10)H(8)N(2)·C(2)H(4)N(4)S, was obtained unexpectedly by reaction of Zn(NO(3))(2)·6H(2)O, NH(4)BF(4) with 3-amino-1,2,4-triazole-5-thione (3-AMT) and 4,4'-bipyridine in water. The dihedral angle between the pyridine rings in the 4,4'-bipyridine molecule is 17.00 (13)°. In the crystal, N-H⋯N and N-H⋯S hydrogen bonds between the components lead to the formation of a three-dimensional network. Furthermore, the structure features face-to-face π-π stacking inter-actions between the 4,4'-bipyridine and triazole rings, with a centroid-centroid distance of 2.976 (2) Å.

catena-Poly[[[diaqua-(1,10-phenanthroline-κ(2)N,N')zinc]-µ-4,4'-bipyridine-κ(2)N:N'] dinitrate 4,4'-bipyridine hemisolvate monohydrate].

In the title compound, [Zn(C(10)H(8)N(2))(C(12)H(8)N(2))(H(2)O)(2)](NO(3))(2)·0.5C(10)H(8)N(2)·H(2)O, the Zn(II) atom is coordinated in a distorted octa-hedral geometry by two N atoms from two 4,4'-bipyridine (4,4'-bipy) ligands, two N atoms from a chelating 1,10-phenanthroline ligand and two O atoms from two mutually cis water mol-ecules. The 4,4'-bipy ligands bridge the Zn(II) atoms into a chain structure along [100]. The uncoordinated 4,4'-bipy mol-ecule lies on an inversion center. O-H⋯O and O-H⋯N hydrogen bonds connect the cationic chains, the nitrate anions, the uncoordinated 4,4'-bipy mol-ecules and the water mol-ecules into tow-dimensional networks.

[Far-IR and THz absorption spectra studies of metronidazole, tinidazole and ornidazole].

Metronidazole, tinidazole and ornidazole are 5-nitro-imidazole medicines used particularly for anaerobic bacteria and protozoa infections. The present paper reports that terahertz time-domain spectroscopy (THz-TDS) and Fourier transform infrared spectroscopy (Far-FTIR) were used to measure the fingerprint spectra of metronidazole, tinidazole and ornidazole in the frequency range of 0.9 - 19.5 THz under the room temperature. In addition, THz-TDS was also used to measure the absorption spectra of pure tinidazole and tinidazole tablets from different manufactures between 0.2 and 2.2 THz. In parallel with the experimental study, the cross correlation analysis was applied to compare the array of correlation coefficients between pure tinidazole and different tinidazole tablets. Results show that the method is rapid, simple and accurate to identify their effective chemical compositions and stability when the FTIR and THz spectra data combine with the array of correlation coefficient. Our research provides a visual approach to the standardization and modernization of the quality control in the production and sale of such drugs.

Tetra-kis(triphenyl-phosphane-κP)silver(I) tetra-fluorido-borate.

The title complex, [Ag(C(18)H(15)P)(4)]BF(4), was prepared by the reaction of silver(I) tetra-fluorido-borate and triphenyl-phosphane in the presence of 1,2-bis-(pyridin-2-yl)ethyl-ene. The Ag(I) atom is tetra-hedrally coordinated by four P atoms from triphenyl-phosphane (PPh(3)) ligands. Due to symmetry, the tetra-fluorido-borate anion is disordered over three positions (each with one third occupancy). The tetra-fluorido-borate anion does not coordinate to the Ag(I) atom.

catena-Poly[[(isoquinoline-κN)(triphenylphospane-κP)copper(I)]-µ-thio-cyanato-κN:S].

In the title coordination compound, [Cu(NCS)(C(9)H(7)N)(C(18)H(15)P)](n), the Cu(I) atom is tetra-hedrally coordinated by one N atom from an isoquinoline ligand, one P atom from a triphenyl-phospane ligand, and one N and one S atom from two thio-cyanate anions. The thio-cyanide anions bridge the Cu(I) atoms into a chain along [100]. π-π inter-actions between the pyridine and benzene rings of the isoquinoline ligands connect the chains [centroid-to-centroid distance = 3.722 (3) Å].

5,6-Dimethyl-1,2,4-triazin-3-amine.

In the crystal structure of the title compound, C(5)H(8)N(4), adjacent mol-ecules are connected through N-H⋯N hydrogen bonds, resulting in a zigzag chain along [100]. The amino groups and heterocyclic N atoms are involved in further N-H⋯N hydrogen bonds, forming R(2) (2)(8) motifs.

4,4'-Bipyridine-1,1'-diium bis-(1,3-benzo-thia-zole-2-thiol-ate).

In the title salt, C10H10N2(2+)·2C7H4NS2(-), the complete 4,4'-bipyridine-1,1'-diium dication is generated by a center of symmetry. In the crystal, N-H⋯N hydrogen bonds are observed between the cations and anions.

[Bis[µ-bis-(diphenyl-phosphino)methane-1:2κ(2)P:P']-bis-(nitrito-κ(2)O,O')]disilver(I) acetonitrile disolvate.

The title complex, [Ag(2)(NO(2))(2)(C(25)H(22)P(2))(2)]·2CH(3)CN, is a centrosymmetric dimer in which two bis(diphenylphosphino)methane ligands bridge two Ag(+) ions, forming an eight-membered ring with a short Ag⋯Ag separation of 3.1809 (5) Å. The distorted P(2)O(2) coordination of the cation is completed by two O-donors from a symmetric bidentate chelate NO(2) (-) anion [Ag-O = 2.550 (3) and 2.567 (3) Å].

4,4'-Bipyridine-3,3'-disulfanediyl-bis-(1H-1,2,4-triazole-5-amine) (1/1).

In the title 1:1 adduct, C(10)H(8)N(2)·C(4)H(6)N(8)S(2)·, the components are connected through N-H⋯N hydrogen bonds, leading to a two-dimensional structure. The C-S-S-C torsion angle is -83.6 (1)°. The dihedral angle between pyridine rings is 1.86 (15)°.

[1,3-Bis(diphenyl-phosphan-yl)propane-κP,P'](1,10-phenanthroline-κN,N')copper(I) perchlorate.

The title compound, [Cu(C(12)H(8)N(2))(C(27)H(26)P(2))]ClO(4), crystallizes with two Cu(I) complex cations and two perchlorate anions in the asymmetric unit. Each Cu(I) cation is four-coordinated by two P atoms of a 1,3-bis-(diphenyl-phosphan-yl)propane mol-ecule and two N atoms of a 1,10-phenanthroline ligand, with a coordination geometry that can be considered as distorted tetra-hedral. The crystal studied was twinned with a twin ratio of 0.786 (2):0.214 (2).

An ortho-rhom-bic polymorph of pyrazino-[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile.

The title compound, C(16)H(6)N(6), is a polymorph of the previously reported structure [Kozlov & Goldberg (2008 ▶). Acta Cryst. C64, o498-o501]. Unlike the previously reported monoclinic polymorph (space group P2(1)/c, Z = 8), the title compound reveals ortho-rhom-bic symmetry (space group Pnma, Z = 4). The mol-ecule shows crystallographic mirror symmetry, while the previously reported structure exhibits two independent mol-ecules per asymmetric unit. In the title compound, adjacent mol-ecules are essentially parallel along the c axis and tend to be vertical along the b axis with dihedral angles of 72.02 (6)°. However, in the reported polymorph, the entire crystal structure shows an anti-parallel arrangement of adjacent columns related by inversion centers and the two independent mol-ecules are nearly parallel with a dihedral angle of 2.48 (6)°.

Tetra-kis(triphenyl-phosphane-κP)silver(I) trifluoro-methane-sulfonate dichloro-methane monosolvate.

In the title compound, [Ag(C(18)H(15)P)(4)]CF(3)O(3)S·CH(2)Cl(2), the Ag atom is coordinated by four P atoms from four PPh(3) ligands. The P-Ag-P angles are in the range 108.02 (6)-110.15 (6)°, which confirms the distorted tetra-hedral environment around the Ag atom.