Preparation and characterization of conducting trimetallic nickel-dithiolene complexes with bridging tetrathiooxalate ligands

Trimetallic nickel dithiolene complexes with two tetrathiooxalate (tto) ligands were obtained by a reaction monitored by ESI-mass spectrometry followed by HPLC separation and were characterized by elemental or crystal structural analysis, MO calculations, and electrical conductivity measurements.     

Liquid chromatographic analysis of cinchona alkaloids in beverages

A method for the determination of Cinchona extract (whose main components are the alkaloids cinchonine, cinchonidine, quinidine, and quinine) in beverages by liquid chromatography was developed. A beverage with an alcohol content of more than 10% was loaded onto an OASIS HLB solid-phase extraction cartridge, after it was adjusted to pH 10 with 28% ammonium hydroxide. Other beverages were centrifuged at 4000 rpm for 5 min, and the supernatant was loaded onto the cartridge. The cartridge was washed with water followed by 15% methanol, and the Cinchona alkaloids were eluted with methanol. The Cinchona alkaloids in the eluate were chromatographed on an L-column ODS (4.6 mm id x 150 mm) with methanol and 20 mmol/L potassium dihydrogen phosphate (3 + 7) as the mobile phase. Cinchona alkaloids were monitored with an ultraviolet (UV) detector at 230 nm, and with a fluorescence detector at 405 nm for cinchonine and cinchonidine and 450 nm for quinidine and quinine (excitation at 235 nm). The calibration curves for Cinchona alkaloids with the UV detector showed good linearity in the range of 2-400 microg/mL. The detection limit of each Cinchona alkaloid, taken to be the concentration at which the absorption spectrum could be identified, was 2 microg/mL. The recovery of Cinchona alkaloids added at a level of 100 microg/g to various kinds of beverages was 87.6-96.5%, and the coefficients of variation were less than 3.3%. A number of beverage samples, some labeled to contain bitter substances, were analyzed by the proposed method. Quinine was detected in 2 samples of carbonated beverage.     

Comparison of accuracy of intravoxel incoherent motion and apparent diffusion coefficient techniques for predicting malignancy of head and neck tumors using half-Fourier single-shot turbo spin-echo diffusion-weighted imaging

Purpose

To evaluate the use of the intravoxel incoherent motion (IVIM) technique in half-Fourier single-shot turbo spin-echo (HASTE) diffusion-weighted imaging (DWI), and to compare its accuracy to that of apparent diffusion coefficient (ADC) to predict malignancy in head and neck tumors.

Patients and methods

HASTE DW images of 33 patients with head and neck tumors (10 benign and 23 malignant) were evaluated. Using the IVIM technique, parameters (D, true diffusion coefficient; f, perfusion fraction; D*, pseudodiffusion coefficient) were calculated for each tumor. ADC values were measured over a range of b values from 0 to 1000 s/mm². IVIM parameters and ADC values in benign and malignant tumors were compared using Student's t test, receiver operating characteristics (ROC) analysis, and multivariate logistic regression modeling.

Results

Mean ADC and D values of malignant tumors were significantly lower than those of benign tumors (P < 0.05). Mean D* values of malignant tumors were significantly higher than those of benign tumors (P < 0.05). There was no significant difference in mean f values between malignant and benign tumors (P > 0.05). The technique of combining D and D* was the best for predicting malignancy; accuracy for this model was higher than that for ADC.

Conclusions

The IVIM technique may be applied in HASTE DWI as a diagnostic tool to predict malignancy in head and neck masses. The use of D and D* in combination increases the diagnostic accuracy in comparison with ADC.     

Development of SI-traceable C-peptide certified reference material NMIJ CRM 6901-a using isotope-dilution mass spectrometry-based amino acid analyses

A certified reference material (CRM) is a higher-order calibration material used to enable a traceable analysis. This paper describes the development of a C-peptide CRM (NMIJ CRM 6901-a) by the National Metrology Institute of Japan using two independent methods for amino acid analysis based on isotope-dilution mass spectrometry. C-peptide is a 31-mer peptide that is utilized for the evaluation of β-cell function in the pancreas in clinical testing. This CRM is a lyophilized synthetic peptide having the human C-peptide sequence, and contains deamidated and pyroglutamylated forms of C-peptide. By adding water (1.00 ± 0.01) g into the vial containing the CRM, the C-peptide solution in 10 mM phosphate buffer saline (pH 6.6) is reconstituted. We assigned two certified values that represent the concentrations of total C-peptide (mixture of C-peptide, deamidated C-peptide, and pyroglutamylated C-peptide) and C-peptide. The certified concentration of total C-peptide was determined by two amino acid analyses using pre-column derivatization liquid chromatography-mass spectrometry and hydrophilic chromatography-mass spectrometry following acid hydrolysis. The certified concentration of C-peptide was determined by multiplying the concentration of total C-peptide by the ratio of the relative area of C-peptide to that of the total C-peptide measured by liquid chromatography. The certified value of C-peptide (80.7 ± 5.0) mg/L represents the concentration of the specific entity of C-peptide; on the other hand, the certified value of total C-peptide, (81.7 ± 5.1) mg/L can be used for analyses that does not differentiate deamidated and pyroglutamylated C-peptide from C-peptide itself, such as amino acid analyses and immunochemical assays.     

A combined micromagnetic-microfluidic device for rapid capture and culture of rare circulating tumor cells

Here we describe a combined microfluidic-micromagnetic cell separation device that has been developed to isolate, detect and culture circulating tumor cells (CTCs) from whole blood, and demonstrate its utility using blood from mammary cancer-bearing mice. The device was fabricated from polydimethylsiloxane and contains a microfluidic architecture with a main channel and redundant 'double collection' channel lined by two rows of dead-end side chambers for tumor cell collection. The microdevice design was optimized using computational simulation to determine dimensions, magnetic forces and flow rates for cell isolation using epithelial cell adhesion molecule (EpCAM) antibody-coated magnetic microbeads (2.8 μm diameter). Using this device, isolation efficiencies increased in a linear manner and reached efficiencies close to 90% when only 2 to 80 breast cancer cells were spiked into a small volume (1.0 mL) of blood taken from wild type mice. The high sensitivity visualization capabilities of the device also allowed detection of a single cell within one of its dead-end side chambers. When blood was removed from FVB C3(1)-SV40 T-antigen mammary tumor-bearing transgenic mice at different stages of tumor progression, cells isolated in the device using anti-EpCAM-beads and magnetically collected within the dead-end side chambers, also stained positive for pan-cytokeratin-FITC and DAPI, negative for CD45-PerCP, and expressed SV40 large T antigen, thus confirming their identity as CTCs. Using this isolation approach, we detected a time-dependent rise in the number of CTCs in blood of female transgenic mice, with a dramatic increase in the numbers of metastatic tumor cells appearing in the blood after 20 weeks when tumors transition to invasive carcinoma and exhibit increased growth of metastases in this model. Importantly, in contrast to previously described CTC isolation methods, breast tumor cells collected from a small volume of blood removed from a breast tumor-bearing animal remain viable and they can be easily removed from these devices and expanded in culture for additional analytical studies or potential drug sensitivity testing.     

Phase behavior of aqueous solutions of copolymers of N,N'-diisopropylfumaramide and N-isopropylacrylamide: effect of the density of side chains

This letter describes the phase behavior of aqueous solutions of an N-isopropylacrylamide (NIPAM) homopolymer and copolymers of N,N'-diisopropylfumaramide (DIPFAM) and NIPAM as studied by transmittance measurements, infrared spectroscopy, and differential scanning calorimetry to reveal the effect of the density of N-isopropylamide side chain upon the phase behavior. The clouding-point and clearing-point temperatures decreased with increasing the mole fraction of DIPFAM (x(D)). It was noteworthy that only an extra side chain per ca. 7 NIPAM units had a remarkable effect on the phase behavior; the interactions between side chains were stronger, the intrapolymer contraction was less favorable, and the cooperativity of phase transition was lower at x(D) = 0.15 presumably because of the steric hindrance of dense side chains.     

A dimethoxytriazine type glycosyl donor enables a facile chemo-enzymatic route toward α-linked N-acetylglucosaminyl-galactose disaccharide unit from gastric mucin

An efficient chemo-enzymatic process for construction of the α-linked disaccharide unit (GlcNAcα1-4Gal) found in gastric mucin has been developed. The process consists of a one-step preparation of a novel triazine type glycosyl donor in water and the subsequent transglycosylation to a galactose derivative catalysed by α-N-acetylglucosaminidase.     

Retinal Photodamage Mediated by All‐trans‐retinal†

Accumulation of all‐trans‐retinal (all‐trans‐RAL), reactive vitamin A aldehyde, is one of the key factors in initiating retinal photodamage. This photodamage is characterized by progressive retinal cell death evoked by light exposure in both an acute and chronic fashion. Photoactivated rhodopsin releases all‐trans‐RAL, which is subsequently transported by ATP‐binding cassette transporter 4 and reduced to all‐trans‐retinol by all‐trans‐retinol dehydrogenases located in photoreceptor cells. Any interruptions in the clearing of all‐trans‐RAL in the photoreceptors can cause an accumulation of this reactive aldehyde and its toxic condensation products. This accumulation may result in the manifestation of retinal dystrophy including human retinal degenerative diseases such as Stargardt’s disease and age‐related macular degeneration. Herein, we discuss the mechanisms of all‐trans‐RAL clearance in photoreceptor cells by sequential enzymatic reactions, the visual (retinoid) cycle, and potential molecular pathways of retinal photodamage. We also review recent imaging technologies to monitor retinal health status as well as novel therapeutic strategies preventing all‐trans‐RAL‐associated retinal photodamage.     

Worst-Case Violation of Sampled Convex Programs for Optimization with Uncertainty

A deterministic approach called robust optimization has been recently proposed to deal with optimization problems including inexact data, i.e., uncertainty. The basic idea of robust optimization is to seek a solution that is guaranteed to perform well in terms of feasibility and near-optimality for all possible realizations of the uncertain input data. To solve robust optimization problems, Calafiore and Campi have proposed a randomized approach based on sampling of constraints, where the number of samples is determined so that only a small portion of the original constraints is violated by the randomized solution. Our main concern is not only the probability of violation, but also the degree of violation, i.e., the worst-case violation. We derive an upper bound of the worst-case violation for the sampled convex programs and consider the relation between the probability of violation and the worst-case violation. The probability of violation and the degree of violation are simultaneously bounded by a prescribed value when the number of random samples is large enough. In addition, a confidence interval of the optimal value is obtained when the objective function includes uncertainty. Our method is applicable to not only a bounded uncertainty set but also an unbounded one. Hence, the scope of our method includes random sampling following an unbounded distribution such as the normal distribution.