Equilibrium structure in the presence of internal rotation: A case study of cis-methyl formate

The Born-Oppenheimer (BO) equilibrium molecular structure () of cis-methyl formate has been determined at the CCSD(T) level of electronic structure theory using Gaussian basis sets of at least quadruple-ζ quality and a core correlation correction. The quadratic, cubic and semi-diagonal quartic force field in normal coordinates has also been computed at the MP2 level employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure () has been derived from experimental ground-state rotational constants and the lowest-order rovibrational interaction parameters calculated from the ab initio cubic force field. To determine structures, it is important to start from accurate ground-state rotational constants. Different spectroscopic methods, applicable in the presence of internal rotation and used in the literature to obtain “unperturbed” rotational constants from the analysis and fitting of the spectrum, are reviewed and compared. They are shown to be compatible though their precision may be different. The and structures are in good agreement showing that, in the particular case of cis-methyl formate, the methyl torsion can still be treated as a small-amplitude vibration. The best equilibrium structure obtained for cis-methyl formate is: r(C_m-O) = 1.434 Å, r(O-C_c) = 1.335 Å, r(C_m-H_s) = 1.083 Å, r(C_m-H_a) = 1.087 Å, r(C_c-H) = 1.093 Å, r(CO) = 1.201 Å, ∠(COC) = 114.4°, ∠(CCH_s) = 105.6°, ∠(CCH_a) = 110.2°, ∠(OCH) = 109.6°, ∠(OCO) = 125.5°, and τ(H_aCOC) = 60.3°. The accuracy is believed to be about 0.001 Å for the bond lengths and 0.1° for the angles.     

Gd complexes of diethylenetriaminepentaacetic acid conjugates of low-molecular-weight chitosan oligosaccharide as a new liver-specific MRI contrast agent

This study was to describe the synthesis of complexes of gadolinium diethylenetriaminepentaacetic acid conjugates of low-molecular-weight chitosan oligosaccharide Gd-DTPA-CSn (n = 6, 8, 11) as a new class of contrast agent as well as its magnetic property in a pilot magnetic resonance imaging. The efficacy of the contrast agent was assessed by measuring the longitudinal relaxivity (r₁), FLASH imaging in phantoms in vitro and signal intensity in vivo of the rat abdominal axial imaging. The r₁ of Gd-DTPA-CS₁₁ was up to 11.65 mM^− 1·s^− 1, which was 3 times higher than that of the analogous MRI contrast agent Gd-DTPA in commercial use. In vivo MR images of rat obtained with Gd-DTPA-CS₁₁ showed strong signal enhancement in liver and the vessels of the liver parenchyma during the extended period of time. The present study suggests that the new synthesized gadolinium complexes can be used as a new class of practical liver-specific MRI contrast agent because of its superior performance compared with Gd-DTPA.     

Assessment of hepatocellular carcinoma using apparent diffusion coefficient and diffusion kurtosis indices: preliminary experience in fresh liver explants

Objectives

The objective was to perform ex vivo evaluation of non-Gaussian diffusion kurtosis imaging (DKI) for assessment of hepatocellular carcinoma (HCC), including presence of treatment-related necrosis, using fresh liver explants.

Methods

Twelve liver explants underwent 1.5-T magnetic resonance imaging using a DKI sequence with maximal b-value of 2000 s/mm². A standard monoexponential fit was used to calculate apparent diffusion coefficient (ADC), and a non-Gaussian kurtosis fit was used to calculate K, a measure of excess kurtosis of diffusion, and D, a corrected diffusion coefficient accounting for this non-Gaussian behavior. The mean value of these parameters was measured for 16 HCCs based upon histologic findings. For each metric, HCC-to-liver contrast was calculated, and coefficient of variation (CV) was computed for voxels within the lesion as an indicator of heterogeneity. A single hepatopathologist determined HCC necrosis and cellularity.

Results

The 16 HCCs demonstrated intermediate-to-substantial excess diffusional kurtosis, and mean corrected diffusion coefficient D was 23% greater than mean ADC (P=.002). HCC-to-liver contrast and CV of HCC were greater for K than ADC or D, although these differences were significant only for CV of HCCs (P≤.046). ADC, D and K all showed significant differences between non-, partially and completely necrotic HCCs (P≤.004). Among seven nonnecrotic HCCs, cellularity showed a strong inverse correlation with ADC (r=−0.80), a weaker inverse correlation with D (− 0.24) and a direct correlation with K (r= 0.48).

Conclusions

We observed non-Gaussian diffusion behavior for HCCs ex vivo; this DKI model may have added value in HCC characterization in comparison with a standard monoexponential model of diffusion-weighted imaging.     

MRI quantification of diffusion and perfusion in bone marrow by intravoxel incoherent motion (IVIM) and non-negative least square (NNLS) analysis

Object

To assess the feasibility of measuring diffusion and perfusion fraction in vertebral bone marrow using the intravoxel incoherent motion (IVIM) approach and to compare two fitting methods, i.e., the non-negative least squares (NNLS) algorithm and the more commonly used Levenberg–Marquardt (LM) non-linear least squares algorithm, for the analysis of IVIM data.

Materials and Methods

MRI experiments were performed on fifteen healthy volunteers, with a diffusion-weighted echo-planar imaging (EPI) sequence at five different b-values (0, 50, 100, 200, 600 s/mm²), in combination with an STIR module to suppress the lipid signal. Diffusion signal decays in the first lumbar vertebra (L1) were fitted to a bi-exponential function using the LM algorithm and further analyzed with the NNLS algorithm to calculate the values of the apparent diffusion coefficient (ADC), pseudo-diffusion coefficient (D*) and perfusion fraction.

Results

The NNLS analysis revealed two diffusion components only in seven out of fifteen volunteers, with ADC = 0.60 ± 0.09 (10^− 3 mm²/s), D* = 28 ± 9 (10^− 3 mm²/s) and perfusion fraction = 14% ± 6%. The values obtained by the LM bi-exponential fit were: ADC = 0.45 ± 0.27 (10^− 3 mm²/s), D* = 63 ± 145 (10^− 3 mm²/s) and perfusion fraction = 27% ± 17%. Furthermore, the LM algorithm yielded values of perfusion fraction in cases where the decay was not bi-exponential, as assessed by NNLS analysis.

Conclusion

The IVIM approach allows for measuring diffusion and perfusion fraction in vertebral bone marrow; its reliability can be improved by using the NNLS, which identifies the diffusion decays that display a bi-exponential behavior.     

Ground-state constants, ab initio anharmonic force field, and equilibrium structure of F2BOH

The millimeterwave spectra of F₂¹⁰BOH and F₂¹¹BOH (difluorohydroxyborane) have been measured in their ground vibrational state. Accurate rotational and centrifugal distortion constants have been determined. The equilibrium geometry and anharmonic force fields have been calculated at the CCSD(T) level of theory. The ab initio centrifugal distortion constants and rotation-vibration interaction constants are compared to the experimental values. Some discrepancies are found and discussed. Particularly, it is explained why the semi-experimental structure is not reliable. The best equilibrium structure is: r_e(BF_cis) = 132.29 pm, r_e(BF_trans) = 131.29 pm, r_e(BO) = 134.48 pm, r_e(OH) = 95.74 pm, ∠_e(FBF) = 118.36°, ∠_e(F_cisBO) = 122.25°, and ∠_e(BOH) = 113.14°.     

Influence of ophthalmic lenses in the illuminance originated at a peripheral glare source and reaching the eye

To study the influence of glare on the visual performance of a subject wearing an ophthalmic lens, it is useful to know how the lens affects the illuminance reaching the eye. In this paper, considering spherical standard ophthalmic lenses and defining the relative illuminance, E_r, as the quotient between the illuminance at the cornea with and without lens, a methodology to evaluate E_r in terms of easily determined parameters is developed. Three effects are considered, pupil size variation of the system with and without lens; lateral shifts of rays transmitted through the lens and reflections at the lens. Calculations are experimentally verified employing 5 organic ophthalmic lenses of ±6; ±4 and 0.12 dioptres and 2 glass plane parallel plates 1.95 and 6.6 mm thick. Using a photometer whose sensor is 12 mm apart from the lens and 740 mm apart from a glare source subtending an eccentricity angle of 9.6°, it results E_r=1.204 for the 6 dioptres lens and E_r=0.803 for the −6 dioptres one if sensor diameter is 10 mm while, for a 719 mm distance and a 10° angle, E_r=0.922 for the thin plate and a 30 mm sensor and E_r=1.006 for the thick plate and a 10 mm sensor. Experimental and theoretical results differ in less than 3%.     

Diffusion-weighted magnetic resonance imaging to evaluate microvascular density after transarterial embolization ablation in a rabbit VX2 liver tumor model

Objective

To evaluate the correlation between findings from diffusion weighted imaging (DWI) and microvascular density (MVD) measurements in VX2 liver tumors after transarterial embolization ablation (TEA).

Materials and Methods

Eighteen New Zealand white rabbits were used in this study. VX2 tumor cells were implanted in livers by percutaneous puncture under computed tomography (CT) guidance. Two weeks later, all rabbits underwent conventional magnetic resonance imaging (MRI) (T1 and T2 imaging), DWI, (b = 100, 600, and 1000 s/mm²) and TEA. MRI was performed again1 week after TEA. Liver tissue was then harvested and processed for hematoxylin and eosin (H&E) staining and immunohistochemical staining for CD31to determine MVD.

Results

VX2 liver tumors were successfully established in all 18 rabbits. Optimal contrast was achieved with a b value of 600 s/mm².The maximum pre-operative apparent diffusion coefficient (ADC)_difference value was 0.28 × 10^− 3 ± 0.10 × 10^− 3 mm²/s, and was significantly different (P < 0.001) from the maximum postoperative ADC_difference value of 0.47 × 10^− 3 ± 0.10 × 10^− 3 mm²/s. However, the mean ADC value for the entire tumor was not significantly correlated with MVD (r = 0.221, P = 0.379), nor was the ADC value for the regions of viable tumor (r = − 0.044, P = 0.862). However, the maximum postoperative ADC_difference value was positively correlated with MVD(r = 0.606, F = 12.247, P = 0.003).

Conclusion

DWI is effective to evaluate the therapeutic efficacy of TEA. The maximum ADC_difference offers a promising new method to noninvasively assess tumor angiogenesis.     

Intra-voxel incoherent motion MRI in rodent model of diethylnitrosamine-induced liver fibrosis

Rationale and Objectives

To compare the apparent diffusion coefficient (ADC) and the perfusion fraction measured by intra-voxel incoherent motion (IVIM) Magnetic Resonance Imaging (MRI) with liver fibrosis degrees in a rodent model.

Materials and Methods

All experiments received approval from our institutional animal care and use committee. Liver fibrosis was induced in 13 rats by oral gavage with diethylnitrosamine; 4 untreated rats with normal livers were used as controls. Diffusion Weighted MRI was performed and 8 gradient factors (0, 50, 100, 150, 200, 300, 400 and 500 s/mm²) were acquired. The values of ADC, true diffusion coefficient D and perfusion fraction f were measured based on Li Bihan’s method. The percentage of liver fibrosis was assessed via quantitative analysis of Masson trichrome staining using an average of 30 fields per section. The MRI measurements were compared to the histological fibrotic grade to evaluate the correlation between them.

Results

ADC contained the contribution of diffusion and perfusion. The ADC and f values decreased significantly with the increasing fibrosis level (correlation coefficient: ADC: ρ = − 0.781, p < 0.001; f: ρ = − 0.720, p = 0.001); but D was poorly correlated with fibrosis level (ρ = − 0.502, p = 0.040).

Conclusion

The hepatic ADC and the perfusion fraction f were significantly correlated with the liver fibrosis level; however, D was not. This might suggest that hepatic perfusion is altered during the progression of hepatic fibrosis.     

Group delay method for MRI aortic pulse wave velocity measurements in clinical protocols with low temporal resolution: Validation in a heterogeneous cohort

BackgroundMRI assessment of aortic pulse wave velocity (PWV) helps predict the risk of vascular events, but the recommended phase contrast sampling rate is faster than what is utilized in most clinical sequences. There are many existing MRI databases obtained for assessment of cardiac output using lower temporal frequency sampling where information might be obtained about aortic stiffness (PWV). In this work, we sought to evaluate whether the Group Delay (GD) method can generate a reproducible measure of stiffness and describe expected age-related stiffening of the aortic arch using lower sampling rates in standard clinical sequences.MethodsPhase contrast (PC) MRI was obtained on the ascending and descending aortic arch in a heterogeneous adult cohort (n = 23; 9 women) spanning over a wide range of ages (ages 24–89, mean 49.4 ± 18.4). Data was collected with standard cardiac MRI protocols for cardiac output evaluation (repetition time = 7.8 ms, views-per-segment = 4, encoding velocity = 200 cm/s). Pulse wave transit times (TT) were computed using the GD method, two other validated automated approaches (cross correlation TT Algorithm by Gaddum and Segment by Medviso), and the manual tangent method. Pressure waveforms from tonometry and flow waveforms from PC MRI were used to assess wave reflections.ResultsGroup Delay and TT-Algorithm showed significant and high retest reproducibility (r = 0.86 for both) as well as high PWV correlation with age (r = 0.93, P-value < 0.00005 and r = 0.96, P-value < 0.00005 respectively) and with each other (r = 0.94, P-value < 0.00001, RMSE = 0.94 m/s). Arbitrary altering of the image acquisition trigger in the GD method introduced error of 10%–13%, but the TT-algorithm error range was 11%–25%.ConclusionGroup Delay enables reproducible assessment of transit time to derive PWV from low temporal resolution clinical cardiac MRI sequences that can also identify age-related stiffening.     

Pockels effect of water in the electric double layer at the interface between water and transparent electrode

We have obtained the first experimental evidence for the Pockels effect of water, which is induced by a high electric field in the electric double layer (EDL) on the water-transparent electrode interface. The electric-field induced energy shift of the visible interference fringes of a 300 nm indium-tin-oxide (ITO) electrode layer is observed, indicating a negative refractive index change at the interface. Numerical calculation reproduces well the experimental observation, showing that the signal mainly originates from water in the EDL. The Pockels constants of water are estimated to be r₃₃ = 5.1 × 100 pm/V and r₁₃ = 1.7 × 100 pm/V. The large anisotropy of the Pockels effect of water is deduced from the incidence angle dependence of the p-polarization signal. At the same time, the ITO shows a blue shift of the band gap in the UV due to the band population effect in the space charge layer. The plasma frequency in the near IR is also expected to increase due to the band population effect, since the ITO has a high doped carrier population close to metal. A negative refractive index change in the ITO space charge layer is induced from both effects, but its effect on the signal is estimated to be much smaller than that of the negative refractive index change of water in the EDL.     

A theoretical study of FeNC in the Δ electronic ground state

We report an ab initio calculation, at the MR-SDCI + Q + E_rel/[Roos ANO (Fe), aug-cc-pVQZ (C, N)] level of theory, of the potential energy surface for ⁶Δ_i FeNC. From the ab initio results, we have computed values for the standard spectroscopic parameters of FeN¹²C and FeN¹³C. Analytical representations of the potential energy surfaces have been fitted through the ab initio points, and the resulting functions have been used for directly solving the rotation-vibration Schrödinger equation by means of the MORBID program and by means of an adiabatic-separation method. For ⁶Δ_i FeNC, our ab initio calculations show that the equilibrium structure is linear with r_e (Fe-N) = 1.9354 Å and r_e (N-C) = 1.1823 Å. We find that the bending potential is very shallow, and the MORBID calculations show that the zero-point averaged structure is bent with the expectation values 〈r (Fe-N)〉 = 1.9672 Å, 〈r(N-C)〉 = 1.1866 Å, and . The experimentally derived bond length r₀ (N-C) = 1.03(8) Å reported for ⁶Δ_i FeNC by Lie and Dagdigian [J. Chem. Phys. 114 (2001) 2137-2143] is much shorter than the corresponding ab initio r_e-value and the averaged value from MORBID. Our calculations suggest that this discrepancy is caused by the inadequate treatment of the large-amplitude bending motion of ⁶Δ_i FeNC. It would appear that for floppy triatomic molecules such as FeNC, r₀-values have little physical meaning, at least when they are determined with the effects of the large-amplitude bending motion being ignored, i.e., under the assumption that the r₀ structure is linear.     

Assessment of interstitial water content of articular cartilage with T1 relaxation

The interstitial water content typically increases in the early degeneration of articular cartilage. Previously, T₂ relaxation has been related to water content, yet it is known to be strongly affected by the collagen orientation. Articular cartilage plugs from the bovine patella, femur and tibia (N=20) were mapped for T₁ and T₂ at 9.4 T to test the ability of T₁ relaxation to reflect cartilage water content. As a reference, water and proteoglycan (PG) contents were determined. Significant (P<.01) linear associations were demonstrated between the relaxation rates and tissue water content (R₁: r=−.81, R₂: r=−.60) and PG content (R₁: r=.75). After adjustment for the tissue water content, partial correlation analysis did not show significant associations between the relaxation rates and tissue PG content. After the effect of PGs was removed, significant (P<.05) linear correlation between the relaxation rates and tissue water content (R₁: r=−.48, R₂: r=−.50) was observed. Thus, the spin-lattice relaxation rate is proposed to provide a biomarker for water content in articular cartilage.     

Interrelationships between 3-T-MRI-derived cortical and trabecular bone structure parameters and quantitative-computed-tomography-derivedbone mineral density

Recently, 3-T magnetic resonance imaging (MRI) has been introduced for bone imaging. Through higher signal-to-noise ratios, as compared to 1.5-T MRI, it promises to be a more powerful tool for the assessment of cortical and trabecular bone measures. The goal of our study was to compare MRI-derived cortical and trabecular bone measures to quantitative computed tomography (QCT)-derived bone mineral density (BMD). Using 3-T MRI in 51 postmenopausal women, apparent (app.) measures of bone volume/total volume, trabecular number (Tb.N), trabecular thickness (Tb.Th) and trabecular separation were derived at the distal radius, distal tibia and calcaneus. Cortical thickness (Ct.Th) was calculated at the distal radius and distal tibia. These measures were compared to QCT-derived BMD of the spine, hip and radius. Significant correlations (^?P<.05; ^??P<.001; ^???P<.0001) were found between spine BMD- and MRI-derived Ct.Th (r_radius=.55, ^?P<.05; r_tibia=.67, ^???P<.0001) and app. Tb.N (r_radius=.33, ^?P<.05; r_tibia=.35, ^?P<.05) at the radius and tibia. Furthermore, within the first 10 mm at the radius, an inverse correlation for Ct.Th and app. BV/TV (r_6mm=−.56, P<.001; r_10mm=−.36, P<.05) and app. Tb.Th (r_6mm=−.54, P<.001; r_10mm=−.41, P<.05) was found.     

Diffusion-weighted imaging (DWI) of the spleen in patients with liver cirrhosis and portal hypertension

Objective

The purpose of this study was to assess the influence of liver cirrhosis and portal hypertension on diffusion coefficients of the spleen.

Material and Methods

We retrospectively evaluated 50 patients with liver cirrhosis and 50 patients without any history of liver disease who underwent magnetic resonance imaging of the upper abdomen, including echo planar diffusion-weighted imaging using b values of 50, 300 and 600 mm²/s. Spleen apparent diffusion coefficient (ADC), liver ADC, muscle ADC and normalized spleen ADC (defined as the ratio of spleen ADC to muscle ADC) were compared between cirrhotic patients and patients in the control group and correlated with Child–Pugh stages. Reproducibility was assessed by measuring interclass correlation coefficient (n = 11). Additionally, in eight patients, ADC measurements were performed 1 day before and 3 days after transjugular intrahepatic portosystemic shunt (TIPSS) implantation.

Results

Compared with control subjects, patients with cirrhosis and portal hypertension had significantly higher spleen ADCs (P = .0001). There was a statistically significant correlation between Child–Pugh grade and spleen ADC (Pearson correlation coefficient, observer 1 r = 0.6, P = .0001; observer 2 r = 0.5, P = .0001). After TIPSS implantation, we observed a reduction in spleen ADC values. Spleen ADC measurements showed a high reproducibility (interclass correlation coefficient 0.75, P = .001).

Conclusion

Our data suggest that different stages of liver cirrhosis and portal hypertension correlate with ADC values of the spleen. Furthermore, ADC values of the spleen decrease after TIPSS implantation. Further studies are required to understand the potential clinical values of these observations.     

Recreational runners with patellofemoral pain exhibit elevated patella water content

Increased bone water content resulting from repetitive patellofemoral joint overloading has been suggested to be a possible mechanism underlying patellofemoral pain (PFP). To date, it remains unknown whether persons with PFP exhibit elevated bone water content. The purpose of this study was to determine whether recreational runners with PFP exhibit elevated patella water content when compared to pain-free controls. Ten female recreational runners with a diagnosis of PFP (22 to 39 years of age) and 10 gender, age, weight, height, and activity matched controls underwent chemical-shift-encoded water-fat magnetic resonance imaging (MRI) to quantify patella water content (i.e., water-signal fraction). Differences in bone water content of the total patella, lateral aspect of the patella, and medial aspect of the patella were compared between groups using independent t tests. Compared with the control group, the PFP group demonstrated significantly greater total patella bone water content (15.4 ± 3.5% vs. 10.3 ± 2.1%; P = 0.001), lateral patella water content (17.2 ± 4.2% vs. 11.5 ± 2.5%; P = 0.002), and medial patella water content (13.2 ± 2.7% vs. 8.4 ± 2.3%; P < 0.001). The higher patella water content observed in female runners with PFP is suggestive of venous engorgement and elevated extracellular fluid. In turn, this may lead to an increase in intraosseous pressure and pain.     

Large amplitude bending motion in CsOH, studied through ab initio-based three-dimensional potential energy functions

The large-amplitude bending motion in CsOH, a ‘classical’ molecule whose microwave spectrum was first recorded in 1967, has been studied ab initio. The three-dimensional potential energy surface has been calculated at the RCCSD(T)_DK3/[QZP + g ANO-RCC (Cs, O, H)] level of theory and employed in MORBID calculations of the rotation-vibration energies and intensities. The ground electronic state is ¹Σ⁺ with the equilibrium structure r_e(Cs-O) = 2.3930 Å, r_e(O-H) = 0.9587 Å, and ∠_e(Cs-O-H) = 180.0°. The O-H moiety is bound to Cs by an ionic bond and the molecule can be described as Cs^δ+(OH)^δ-. Hence, the bending potential is shallow and gives rise to large-amplitude bending motion. The ro-vibrationally averaged structural parameters, determined as expectation values over MORBID wavefunctions, are 〈r(Cs-O)〉₀ = 2.3987 Å, 〈r(O-H)〉₀ = 0.9754 Å, and 〈∠(Cs-O-H)〉₀ = 163°. Although the averaged structure in the vibrational ground state is far from being linear, the Yamada-Winnewissi-linearity parameter for CsOH is γ₀≈-1.0, the value characteristic for a linear molecule.     

Synthesis of water-soluble FeOOH nanospindles and their performance for magnetic resonance imaging

Water soluble FeOOH nanospindles with small size were synthesized by a simple hydrolysis method of inorganic salts and water bath treatment with different incubation time. The morphology, microstructure, magnetic resonance imaging (MRI) performance and cytotoxicity of the as-prepared FeOOH nanospindles were investigated, respectively. The results showed that the longitudinal length of FeOOH nanospindles was about 40-50 nm, and the incubation time had important effect for the morphology and production rate of FeOOH nanospindles. MRI test showed that the longitudinal and transverse relaxivities (r₁ and r₂ values) of FeOOH nanospindles were about 3.06 mM⁻¹ s⁻¹ and 5.06 mM⁻¹ s⁻¹, respectively. Furthermore, the experimental results of the Prussian Blue staining showed the clusters of FeOOH nanospindles in the cytoplasm of the labeled cells, and the cytotoxicity characterization indicated that FeOOH nanospindles have low cytotoxicity. Therefore, the as-prepared FeOOH nanospindles will have potential applications as T₁- and T₂-weighted MRI contrast agents.     

Hepatic lipid composition analysis using 3.0-T MR spectroscopy in a steatotic rat model

Purpose

To investigate the feasibility of in vivo assessment of hepatic lipid composition using 3.0-T proton magnetic resonance spectroscopy (¹H-MRS) in a steatotic rat model and compare it to histopathological and biochemical assessment.

Materials and Methods

Hepatic steatosis was induced by feeding rats with a methionine/choline-deficient (MCD) diet for 1, 2, 3, 5 or 7 weeks (n=5 per group). At the end of the diet period, ¹H-MRS of the liver was performed, and rats were sacrificed for histopathological and biochemical assessment of the liver. Spectra were acquired in a single voxel (1.2 cc) using a point-resolved spectroscopic sequence with TE/TR=35/2000 ms and 64 signal acquisitions. From the MR spectra, peak area ratios were calculated to estimate hepatic lipid composition.

Results

During MCD diet periods, hepatic steatosis significantly increased on histopathology (P<.001). The ¹H-MRS measurements of total hepatic fat content [1.3/(1.3+4.65) ppm] correlated strongly with histological macrovesicular hepatic steatosis (r=0.93, P<.001) and with the biochemical total hepatic fatty acids (r=0.94, P<.001). Total unsaturated fatty acids [TUFA, 5.4/(1.3+4.65) ppm] estimated with ¹H-MRS strongly correlated with the biochemical unsaturated fatty acids (r=0.90, P<.001). Polyunsaturated fatty acids [PUFA, 2.8/(1.3+4.65) ppm] estimated with ¹H-MRS strongly correlated with biochemical PUFA (r=0.91, P<.001). The proportion of total unsaturated fatty acids relative to the amount of total fatty acids (rTUFA, 5.4/1.3ppm) measured with ¹H-MRS strongly correlated with the biochemical amount of unsaturated relative to total hepatic fatty acids (r=0.81, P<.001). The proportion of PUFA relative to the amount of total fatty acids (rPUFA, 2.8/1.3 ppm) measured with ¹H-MRS correlated with the biochemical amount of PUFA relative to total fatty acids (r=0.59, P=0.005,) and with the biochemical amount of omega-6 PUFA relative to total fatty acids (r=0.73, P<.001).PUFA at ¹H-MRS correlated with the histopathologically assessed degree of lobular inflammation in the liver (r=0.57, P=.001).

Conclusion

3.0T ¹H-MRS is able to measure poly- and unsaturated hepatic fatty acids and this strongly correlates with biochemical assessment. This study provides evidence that 3.0-T ¹H-MRS is a noninvasive technique to assess hepatic lipid composition.     

A theoretical study of BrCN in the Π electronic ground state: Large amplitude bending motion

We have calculated the three-dimensional potential energy surfaces for the 1 ²A′ and 1 ²A″ states of BrCN⁺ at the MR-SDCI_DK+Q/[QZP-ANO-RCC (Br, C, N)] level of theory, where MR-SDCI_DK means ‘multi-reference single and double excitation configuration interaction calculation with Douglas-Kroll Hamiltonian.’ These ab initio potential energy surfaces have a common minimum (corresponding to the state) at a linear equilibrium structure with r_e(Br-C) = 1.735 Å and r_e(C-N) = 1.199 Å. Variational RENNER calculations yield a zero-point averaged structure (with the structural parameters calculated as expectation values over rovibrational wavefunctions) with 〈r(Br-C)〉₀ = 1.739 Å, 〈r(C-N)〉₀ = 1.204 Å, and 〈∠(Br-C-N)〉₀ = 172(4)°. A severe Fermi resonance between 2ν₂ and ν₃ has been found theoretically for the ²A″ potential energy surface. Comparing the ab initio zero-point averaged structure with a recent, experimentally derived r₀ structure, it is concluded that the effects of large-amplitude bending motion should be taken into account explicitly in the process of deriving the r₀ structure from the experimental values of the rotational constants. The electronic structure of BrCN⁺ has also been discussed.     

Water proton density in human cortical bone obtained from ultrashort echo time (UTE) MRI predicts bone microstructural properties

PurposeTo investigate the correlations between cortical bone microstructural properties and total water proton density (TWPD) obtained from three-dimensional ultrashort echo time Cones (3D-UTE-Cones) magnetic resonance imaging techniques.Materials and methods135 cortical bone samples were harvested from human tibial and femoral midshafts of 37 donors (61 ± 24 years old). Samples were scanned using 3D-UTE-Cones sequences on a clinical 3T MRI and on a high-resolution micro-computed tomography (μCT) scanner. TWPD was measured using 3D-UTE-Cones MR images. Average bone porosity, pore size, and bone mineral density (BMD) were measured from μCT images at 9 μm voxel size. Pearson's correlation coefficients between TWPD and μCT-based measures were calculated.ResultsTWPD showed significant moderate correlation with both average bone porosity (R = 0.66, p < 0.01) and pore size (R = 0.57, p < 0.01). TWPD also showed significant strong correction with BMD (R = 0.71, p < 0.01).ConclusionsThe presented 3D-UTE-Cones imaging technique allows assessment of TWPD in human cortical bone. This quick UTE-MRI-based technique was capable of predicting bone microstructure differences with significant correlations. Such correlations highlight the potential of UTE-MRI-based measurement of bone water proton density to assess bone microstructure.