Sodium visibility and quantitation in intact bovine articular cartilage using high field (23)Na MRI and MRS

Noninvasive methods of detecting cartilage degeneration can have an impact on identifying the early stages of osteoarthritis. Accurate measurement of sodium concentrations within the cartilage matrix provides a means for analyzing tissue integrity. Here a method is described for quantitating sodium concentration and visibility in cartilage, with general applications to all tissue types. The sodium concentration in bovine patellar cartilage plugs was determined by three different methods: NMR spectroscopy of whole cartilage plugs, NMR spectroscopy of liquefied cartilage in concentrated HCl, and inductively coupled plasma emission spectroscopy. Whole bovine patellae were imaged with relaxation normalized calibration phantoms to ascertain sodium concentrations inside the articular cartilage. Sodium concentrations in intact articular cartilage were found to range from approximately 200 mM on the edges to approximately 390 mM in the center, with an average of approximately 320 mM in five separate bovine patellae studied. In essence, we have created sodium distribution maps of the cartilage, showing for the first time, spatial variations of sodium concentration in intact cartilage. This average concentration measurement correlates very well with the values obtained from the spectroscopic methods. Furthermore, sodium was found to be 100% NMR visible in cartilage plugs. Applications of this method in diagnosing and monitoring treatment of osteoarthritis are discussed.     

Time-domain quantification of multiple-quantum-filtered (23)Na signal using continuous wavelet transform analysis

The application of continuous wavelet transform (CWT) analysis technique is presented to analyze multiple-quantum-filtered (MQF) (23)Na magnetic resonance spectroscopy (MRS) data. CWT acts on the free-induction-decay (FID) signal as a time-frequency variable filter. The signal-to-noise ratio (SNR) and frequency resolution of the output filter are locally increased. As a result, MQF equilibrium longitudinal magnetization and the apparent fast and slow transverse relaxation times are accurately estimated. A developed iterative algorithm based on frequency signal detection and components extraction, already proposed, was used to estimate the values of the signal parameters by analyzing simulated time-domain MQF signals and data from an agarose gel. The results obtained were compared to those obtained by measurement of signal height in frequency domain as a function of MQF preparation time and those obtained by a simple time-domain curve fitting. The comparison indicates that the CWT approach provides better results than the other tested methods that are generally used for MQF (23)Na MRS data analysis, especially when the SNR is low. The mean error on the estimated values of the amplitude signal and the apparent fast and slow transverse relaxation times for the simulated data were 2.19, 6. 63, and 16.17% for CWT, signal height in frequency domain, and time-domain curve fitting methods, respectively. Another major advantage of the proposed technique is that it allows quantification of MQF (23)Na signal from a single FID and, thus, reduces the experiment time dramatically.     

T1ρ-weighted MRI using a surface coil to transmit spin-lock pulses

T1rho-weighted MRI is a novel basis for generating tissue contrast. However, it suffers from sensitivity to B1 inhomogeneity. First, excitation with a spatially varying B1 causes flip-angle artifacts and second, spin locking with an inhomogeneous B1 results in non-uniform T1rho contrast. In this study, we overcome the former complication with a specially designed spin-locking pulse sequence and we successfully obtain T1rho-weighted images with a surface coil. In this pulse sequence, the spin-lock pulse was divided into segments of equal duration and alternating phase. This "self-compensating" T1rho-preparatory pulse sequence was analyzed and the effect of an inhomogeneous B1 field was simulated using the Bloch equations. T1rho-weighted MR images of a phantom and a human knee joint in vivo were obtained on a clinical scanner with a surface coil to demonstrate the utility of the pulse sequence. The self-compensating T1rho-prepared pulses sequence resulted in substantially reduced image artifacts compared to the conventional, single-phase spin-lock pulse.     

Synthesis,characterization and electrochemical properties of copper(II) complexes derived from succinoyldihydrazine Schiff base ligands

Four new copper(II) complexes of the composition [Cu(H₂L)(H₂O)] have been synthesized by template method from reaction of copper(II) acetate, succinoyldihydrazine and some o-hydroxy aromatic aldehydes and ketones in aqueous methanol media. The composition of the complexes has been established on the basis of data obtained from analytical and mass spectral studies. The structure of the complexes has been discussed in the light of molar conductance, magnetic moment, Uv-vis, EPR and IR spectral studies. All of the complexes are non-electrolyte in DMSO. The μ_eff values for the complexes fall in the region 1.76–1.85 BM which rules out the possibility of any M–M interaction in the structural unit of the complexes. The ligands coordinate to the metal centre in enol form through phenolate/naphtholate oxygen atoms and azomethine nitrogen atoms. The NMR spectra show that ligands are present in anti-cis configuration in uncoordinated state. In all of the complexes the copper centre adopts square pyramidal stereochemistry. The unpaired electron is present in $d_{x^2-y^2}$ orbital in the ground state for copper centre in the complexes. The electron transfer reactions for the complexes have been studied by cyclic voltammetry.     

A new method for the oxidation of 2-Keto-1,2,3,4-tetrahydro-quinoxaline,investigations on the complex formed between 2-hydroxyquinoxaline and cuprous chloride

2-Keto-1,2,3,4-tetrahydroquinoxaline I is rapidly oxidised to 2-hydroxyquinoxaline II on reaction with cupric chloride. This is an oxidation-reduction reaction in which the cupric chloride in the process is reduced to cuprous chloride. The latter instantaneously reacts with II forming an insoluble brick red complex. Compound II can be regenerated from the complex by treatment with alkali. The properties of this new complex are discussed.     

Mass spectral studies of alkylbenzenesulphonic acids through their S-benzylisothiouronium salts

The mass spectra of alkylbenzenesulphonic acids in the form of their S-benzylisothiouronium salts have been studied. These S-benzylisothiouronium salts dissociated into two parent reactant ions: (i) alkylbenzenesulphonic acid and (ii) S-benzylisothiourea. The characteristic fragmentation patterns of alkylbenzenesulphonic acids (0-5 substituted alkyls) were studied and compared with those of the parent hydrocarbons. The intensity of the molecular ion peak decreased with the increase in the molecular weight of the sulphonic acids. Desulphonation as well as loss of the alkyl group was observed in all the spectra. Migration of the alkyl group from S to O, followed by degradation, was also observed in all the spectra studied.     

Characterization of heterobimetallic and mixed-valence complexes of molybdenum(V) derived from bis(2-hydroxy-1-naphthaldehyde) malonoyldihydrazone

Heterobimetallic complexes [UO₂Mo^V(CH₂L)(hzd)(H₂O)₂] _n , [ZnMo^V(CH₂L)(hzd)(H₂O)₂] _n and mixedvalence complexes [Mo^VIO₂Mo^V(CH₂L)(hzd)(H₂O)₂] _n (where hzdH₃ = inhH₃, n = 1; slhH₃, n = 2) are synthesized from bis(2-hydroxy-1-naphthaldehyde)malonoyldihydrazone (CH₂LH₄) and monometallic precursor complexes [Mo(CH₂LH₂)(hzd)]·nH₂O (n = 0, 1) in ethanol. The composition of the complexes is established based on the data obtained from the elemental analysis. The structure of the complexes is discussed in the light of data obtained from molar conductance, magnetic moment, electronic, EPR, and IR spectroscopic studies. All complexes have ??B values in the range 1.59?C1.64 B.M., slightly lower than that required for one unpaired electron. The heterobimetallic complexes show two bands, while mixed-valence complexes show only one band in the visible region assigned to the d-d transition. The g-values decrease in going from uranyl-to-molybdenyl-to-zinc complexes containing the isonicotinoyldiazenido (inh) group, however, no such regular trend is observed in the case of complexes containing the salicyloyldiazenido (slh) group in the coordination sphere. In all complexes, the principal dihydrazone ligand is present in the enol form as a bridging hexadentate ligand in the anti-cis configuration where hydrazide ligands are coordinated to the metal centre as a trinegative bidentate ligand in the diazenido form.     

Synthesis and Antifungal Activities of Some New 5,7‐Disubstituted[1,2,4]Triazolo[1,5‐a]Pyrimidin‐6‐one Derivatives

Synthesis of a new series of [1,2,4]triazolo[1,5‐a]pyrimidin‐6‐one by [4 + 2]cycloaddition reaction of 3‐benzylidineamino[1,2,4]triazole with monophenyl ketene and diphenyl ketene generated in situ from phenylacetyl chloride and diphenylacetyl chloride in the presence of triethylamine is described. The newly synthesized compounds were also tested for antifungal activities against Rhizoctonia solani and Trichoderma sp.     

Time resolved studies on X-rays and charged particles emission from a low energy plasma focus device

The time resolved studies on soft X-ray, hard X-ray, electron beam and ion beam emissions from a low energy plasma focus device are carried out simultaneously by employing a photodiode X-ray spectrometer, a scintillator photomultiplier tube, a combination of Faraday cup and Rogowski coil assembly and a biased Faraday cup, respectively. The soft X-ray is seen to be emitted in short multiple pulses corresponding to different pinch stages where as it is a single for hard X-ray, which corresponds to only maximum pinch stage. Similarly, multiple pulses of electron beam is found, which also corresponds to different pinch stages and these pulses are analogous with the soft X-ray pulses. The effective hard X-ray photon energy is estimated by foil absorption technique and found to be around 110 keV, which is consistent with the observed electron beam energy distribution. The simultaneous investigation of the electron and ion beam shows that both are accelerated by the same local field generated during the pinching process. The detailed results of time resolved studies on various radiations are incorporated in this Letter.     

Artifacts in T1 rho-weighted imaging: compensation for B(1) and B(0) field imperfections

The origin of spin locking image artifacts in the presence of B(0) and B(1) magnetic field imperfections is shown theoretically using the Bloch equations and experimentally at low (omega(1) < Delta omega(0)), intermediate (omega(1) approximately Delta omega(0)) and high (omega(1) > Delta omega(0)) spin locking field strengths. At low spin locking fields, the magnetization is shown to oscillate about an effective field in the rotating frame causing signature banding artifacts in the image. At high spin lock fields, the effect of the resonance offset Deltao mega(0) is quenched, but imperfections in the flip angle cause oscillations about the omega(1) field. A new pulse sequence is presented that consists of an integrated spin echo and spin lock experiment followed by magnetization storage along the -z-axis. It is shown that this sequence almost entirely eliminates banding artifacts from both types of field inhomogeneities at all spin locking field strengths. The sequence was used to obtain artifact free images of agarose in inhomogeneous B(0) and B(1) fields, off-resonance spins in fat and in vivo human brain images at 3 T. The new pulse sequence can be used to probe very low frequency (0-400 Hz) dynamic and static interactions in tissues without contaminating B(0) and B(1) field artifacts.