Ab initio calculation of magnetic anisotropy and thermal spin transition in the variable temperature crystal conformations of [Co(terpy)2]2.

The structure-property correlation of [Co(terpy)2]2+, which shows a spin crossover at 270 K, has been computationally investigated based on its variable temperature crystal structures. Among the employed DFT functionals, only the re-parametrized hybrid B3LYP* functional could describe the correct spin transition temperature. Explicit consideration of metal-ligand sigma bonding with dynamic electron correlation is found to be necessary for an accurate determination of the SCO temperature with multi-reference calculations. The metal-ligand axial bond distances are found to be the most significant internal coordinates in deciding SCO. A small structural change along the axial distance causes a change in the t2g orbital splitting pattern and a reorientation of the magnetization axes at the SCO temperature. The complex shows an unusual triaxial magnetic anisotropy, with an easy axis of magnetization developing at higher temperatures. The strong coupling of low-frequency wagging motion of the two terpyridine ligands with the spin states of the complex provides an effective pathway for the relaxation of magnetization, resulting in a small magnetic anisotropy barrier.

2-Anilidomethylpyridine-Derived Three-Coordinate Zinc Hydride: The Journey Unveils Anilide Backbone's Reactive Nature.

Low-coordinate heteroleptic zinc hydrides are catalytically important but rare and synthetically challenging. We herein report three-coordinate monomeric zinc hydride on a 2-anilidomethylpyridine framework (NNL). The synthetic success comes through systematically screening a few different routes from different precursors. During the process, the ligand's anilide backbone interestingly appears to be more reactive than Zn's terminal site to electrophilic Lewis and Brønsted acids. The proligand NNLH reacts with [Zn{N(SiMe3)2}2] and ZnEt2 to give [(NNL)ZnA] (A = N(SiMe3)2 (1), Et(2)). Both are inert to PhSiH3 and H2 but react with HBpin only through the internal Zn-Nanilide bond to give the borylated ligand NNLBpin (3). The reactions of 1 and 2 with Ph3EOH (E = C, Si) afford a series of divergent compounds like [(NNLH)Zn(OSiPh3)2] (4), [Zn3(OSiPh3)4Et2] (5), and [EtZn(OCPh3)] (6). But in all cases, it is invariably the Zn-Nanilide bond protonated by the -OH with equal or higher preference than the terminal Zn-N or Zn-C bonds. A DFT analysis rationalizes the origin of such a reactivity pattern. Realizing that an acid-free route might be the key, reacting [(NNL)Li] with ZnBr2 gives [(NNL)Zn(µ-Br)]2 (7), which on successively treating with KOSiPh3 and PhSiH3 gives the desired [(NNL)ZnH] (8) as a three-coordinate monomer with a terminal Zn-H bond. Estimating the ligand steric in 8 shows the openness in Zn's coordination sphere, a desired criterion for efficient catalysis. This and a positive influence of the pyridyl sidearm is reflected in 8's superior activity in hydroborating PhC(O)Me by HBpin in comparison to Jones' two-coordinate anilido zinc hydride.

Spin-state energetics and magnetic anisotropy in penta-coordinated Fe(III) complexes with different axial and equatorial ligand environments.

The penta-coordinated trigonal-bi-pyramidal (TBP) Fe(III) complex (PMe2Ph)2FeCl3 shows a reduced magnetic anisotropy in its intermediate-spin (IS) state as compared to its methyl-analog (PMe3)2Fe(III)Cl3. In this work, the ligand environment in (PMe2Ph)2FeCl3 is systematically altered by replacing the axial -P with -N and -As, the equatorial -Cl with other halides, and the axial methyl group with an acetyl group. This has resulted in a series of Fe(III) TBP complexes modelled in their IS and high-spin (HS) states. Lighter ligands -N and -F stabilize the complex in the HS state, while the magnetically anisotropic IS state is stabilized by -P and -As at the axial site, and -Cl, -Br, and -I at the equatorial site. Larger magnetic anisotropies appear for complexes with nearly degenerate ground electronic states that are well separated from the higher excited states. This requirement, largely controlled by the d-orbital splitting pattern due to the changing ligand field, is achieved with a certain combination of axial and equatorial ligands, such as -P and -Br, -As and -Br, and -As and -I. In most cases, the acetyl group at the axial site enhances the magnetic anisotropy compared to its methyl counterpart. In contrast, the presence of -I at the equatorial site compromises the uniaxial type of anisotropy of the Fe(III) complex leading to an enhanced rate of quantum tunneling of magnetization.

Low-cost preventive screening using carotid ultrasound in patients with diabetes.

Diabetes and atherosclerosis are the predominant causes of stroke and cardiovascular disease (CVD) both in low- and high-income countries. This is due to the lack of appropriate medical care or high medical costs. Low-cost 10-year preventive screening can be used for deciding an effective therapy to reduce the effects of atherosclerosis in diabetes patients. American College of Cardiology (ACC)/American Heart Association (AHA) recommended the use of 10-year risk calculators, before advising therapy. Conventional risk calculators are suboptimal in certain groups of patients because their stratification depends on (a) current blood biomarkers and (b) clinical phenotypes, such as age, hypertension, ethnicity, and sex. The focus of this review is on risk assessment using innovative composite risk scores that use conventional blood biomarkers combined with vascular image-based phenotypes. AtheroEdge™ tool is beneficial for low-moderate to high-moderate and low-risk to high-risk patients for the current and 10-year risk assessment that outperforms conventional risk calculators. The preventive screening tool that combines the image-based phenotypes with conventional risk factors can improve the 10-year cardiovascular/stroke risk assessment.

Determining the occlusal plane using hamular notch incisive papilla plane evaluator: An in vivo study.

AIMS: Identification and establishment of the occlusal plane in patients with impaired occlusal plane, presents a major hurdle for the execution of natural esthetics, speech, and function. The aim of this study was to minimize such errors while occlusal rehabilitation, and employ hamular notchincisive papilla (H.I.P) plane as landmark and scribe it on the cast using H. I. P evaluator and utilise for occlusal corrections. SETTINGS AND DESIGN: HIP plane being parallel to the occlusal plane could ease the operator when it could be scribed on cast to analyze and restore the compromised occlusal plane. MATERIALS AND METHODS: Dentulous casts of two hundred participants were mounted on the Hanau Wide-Vue articulator. Reference points were marked on the maxillary right central incisor and maxillary molars on casts for attaining different occlusal planes, the incisive papilla and hamular notch region were also marked for HIP plane. A plane parallel HIP was scribed on cast using HIP Evaluator. The casts were then scanned using a three-dimensional coordinate measuring machine attached to perception V5 laser scanner and measurements were made using Geomagic X design software. The most parallel occlusal plane to HIP plane was evaluated, and the reliability of HIP evaluator was verified. STATISTICAL ANALYSIS USED: ANOVA test, Post hoc-Bonferroni test, and independent sample "t"-test were carried out for the comparison between occlusal planes, among the genders and for the analysis of the angle of deviation of scribed plane on the cast to HIP plane on the right and left sides. RESULTS: Occlusal plane III (Mesio-labial incisal edge of upper right central incisor to Mesio-buccal cusp tips of upper second molars) showed least angle of deviation with 1.316° ± 1.158° to HIP plane among tested subjects. There is no significant difference between the genders. The plane scribed on the cast with H. I. P evaluator showed relative parallelism to H. I. P plane with minimum deviation of 0.010° ± 0.363°. CONCLUSION: Occlusal plane III is more parallel to H. I. P plane. Scribed plane on the cast using H. I. P evaluator is parallel to H. I. P plane. H. I. P evaluator can be used as an alternative tool to establish the occlusal plane to rehabilitate patient with deficient dentition or disordered occlusal plane.

Evaluation of Natural Tooth Color Space of the Indian Population and Its Comparison to Manufacturer's Shade Systems.

PURPOSE: This study evaluated the natural tooth color space of the Indian population and compared it with the manufacturer's shade systems. MATERIALS AND METHODS: Maxillary central incisors of individuals aged 18-30 years and shade tabs of Vita Lumin vaccum (VL), Vitapan 3D master (V3D), and Shofu's Vintage Halo (SVH) shade guide were digitally photographed under standardized conditions. L*a*b* values from middle part of tooth and shade tab were attained using Adobe Photoshop 7.0 software. Comparative evaluation between the natural teeth and shade tabs was done, and color differences were noted and analyzed using appropriate software. RESULTS: The L*a*b* values of the Indian population displayed a broader range than the shade guides. The mean Δ E* for VL shade guide was 7.22, 7.99 for SVH, and 8.39 for V3D, which was statistically significant. Color space of the Indian population on displayed an elongated cone with an irregular base. The plots of all the three shade guides were narrower and shorter and deficient in the blue-green region as compared to the population. CONCLUSIONS: Within the limitations of this study, the mean color difference between the Indian population and the three shade guides was above the acceptability thresholds (ΔE* = 2.7-6.8). VL, V3D, and SVH shade guides were deficient in their coverage and therefore can be considered inconsistent.

Effect of plant extract denture cleansing on heat-cured acrylic denture base resin: An in vitro study.

AIM: Various chemical solutions have been recommended for denture disinfection; however, the immersion effect on the properties of denture base resin may also have effect on strength of the resin material. The purpose of this in vitro study was to compare and evaluate the flexural strength of heat-cure acrylic denture base resin by combination method of denture cleansing and plant extract immersion. MATERIALS AND METHODS: In this study, ninety specimens of heat-cure acrylic denture base resin material were fabricated with dimensions of 65 mm × 10 mm × 3.3 mm. The specimens were divided into three groups, namely, Group I-III of thirty specimens each and were immersed in distilled water, denture cleanser, and thyme essential oil, respectively. The flexural strength of specimen was evaluated. RESULTS: Natural plant extract showed better flexural strength than immersed in denture cleanser and control group but statistically was not significant. CONCLUSION: The study concluded that plant extract, namely, thyme essential oil, showed better flexural strength than combination method and can be used as denture cleanser.

Commercial and Plant Extract Denture Cleansers in Prevention of Candida albicans Growth on Soft Denture Reliner: In Vitro Study.

OBJECTIVE: To evaluate and compare the efficacy of two plant extracts and two commercially available denture cleansers against candida albicans adherent to soft denture reline material. MATERIALS AND METHODS: In this study 60 specimens of soft denture reliner material specimens were fabricated with dimensions 10x10x2 mm. The sterile specimens were inoculated by immersion in Sabourand broth containing Candida albicans for 16 hours at 37°C in an incubator. Then the specimens were washed and immersed in denture cleansers which were divided into group five groups from Group I-V for CD Clean(®), Nigella sativa, thyme essential oil, Fittydent(®) and distilled water respectively, for 8 hours at room temperature. Then they were washed, fixed with methanol and stained with crystal violet. Candida cells adherent to the specimens were counted under microscope. The number of cells adherent to test samples were compared with that adherent to control. RESULTS: The effectiveness of Fittydent(®) was more than CD Clean(®) in reducing the adherent candida albicans and the difference was statically significant (p = <0.001). Both thyme essential oil and nigella sativa were almost same in effectiveness against candida albicans but the difference was not statically significant (p= 0.79). Post-hoc Tukey's test was performed which indicated that Fittydent® was the most effective amongst the denture cleansers tested in this study, followed by thyme essential oil, nigella sativa and CD Clean(®). CONCLUSION: The results of the study showed that all denture cleansers used in the study were significantly effective. The study indicated that Fittydent is more effective amongst the denture cleansers because of its mechanism of action; however the plant extracts used in this study were also significantly effective against candida albicans.

IMPROVEMENT IN PANCREATIC ß-CELL FUNCTION WITH VITAMIN D AND CALCIUM SUPPLEMENTATION IN VITAMIN D-DEFICIENT NONDIABETIC SUBJECTS.

OBJECTIVE: There are varied reports on the effect of vitamin D supplementation on ß-cell function and plasma glucose levels. The objective of this study was to examine the effect of vitamin D and calcium supplementation on ß-cell function and plasma glucose levels in subjects with vitamin D deficiency. METHODS: Nondiabetic subjects (N = 48) were screened for their serum 25-hydroxyvitamin D (25-OHD), albumin, creatinine, calcium, phosphorus, alkaline phosphatase, and intact parathyroid hormone (PTH) status. Subjects with 25-OHD deficiency underwent a 2-hour oral glucose tolerance test. Cholecalciferol (9,570 international units [IU]/day; tolerable upper intake level, 10,000 IU/day; according to the Endocrine Society guidelines for vitamin D supplementation) and calcium (1 g/day) were supplemented. RESULTS: Thirty-seven patients with 25-OHD deficiency participated in the study. The baseline and post-vitamin D/calcium supplementation and the difference (corrected) were: serum calcium, 9 ± 0.33 and 8.33 ± 1.09 mg/dL (-0.66 ± 1.11 mg/dL); 25-OHD, 8.75 ± 4.75 and 36.83 ± 18.68 ng/mL (28.00 ± 18.33 ng/mL); PTH, 57.9 ± 29.3 and 36.33 ± 22.48 pg/mL (-20.25 ± 22.45 pg/mL); fasting plasma glucose, 78.23 ± 7.60 and 73.47 ± 9.82 mg/dL (-4.88 ± 10.65 mg/dL); and homeostasis model assessment-2-percent ß-cell function C-peptide secretion (HOMA-2-%B C-PEP), 183.17 ± 88.74 and 194.67 ± 54.71 (11.38 ± 94.27). Significant differences were observed between baseline and post-vitamin D/calcium supplementation serum levels of corrected calcium (Z, -3.751; P<.0001), 25-OHD (Z, -4.9; P<.0001), intact PTH (Z, -4.04; P<.0001), fasting plasma glucose (Z, -2.7; P<.007), and HOMA-2-%B C-PEP (Z, -1.923; P<.05) as determined by Wilcoxon signed rank test. Insulin resistance as measured by HOMA was unchanged. CONCLUSION: Optimizing serum 25-OHD concentrations and supplementation with calcium improves fasting plasma glucose levels and ß-cell secretory reserve. Larger randomized control studies are needed to determine if correction of 25-OHD deficiency will improve insulin secretion and prevent abnormalities of glucose homeostasis.

Surface bond strength in nickel based alloys.

Bonding of ceramic to the alloy is essential for the longevity of porcelain fused to metal restorations. Imported alloys used now a days in processing them are not economical. So this study was conducted to evaluate and compare the bond strength of ceramic material to nickel based cost effective Nonferrous Materials Technology Development Center (NFTDC), Hyderabad and Heraenium S, Heraeus Kulzer alloy. An Instron testing machine, which has three-point loading system for the application of load onto the specimen was utilized for analyzing bond strength of both alloys. Student t test was conducted and t value obtained was 0.644, and the mean value of flexural bond strength of indigenous alloy is 81.75 with standard deviation of 12.25 and of imported alloy is 84.42 with standard deviation of 10.35, indicating that there was no significant difference between the two alloys. Due to ever increasing cost of imported non-precious alloy the need for a cost-effective replacement was fulfilled by indigenous NFTDC alloy.

Quantization of Dextromethorphan and Levocetirizine in Combined Dosage form Using a Novel Validated RP-HPLC Method.

The present study reveals a simple isocratic RP-HPLC method for the simultaneous determination of dextromethorphan hydrobromide and levocetirizine dihydrochloride in a cough syrup. The separation of these compounds was achieved within 10 min on a Phenomenex (USA) C(18) analytical column, 250×4.0 mm i.d., using an isocratic mobile phase consisting of potassium dihydrogen phosphate buffer (pH 2.5) - acetonitrile- tetrahydrofuran (70:25:5, v/v/v). The analysis was performed at a flow rate of 1.2 ml/min and at a detection wavelength of 232 nm. Percentage recovery and RSD were 100.36% and 0.05% for levocetirizine dihydrochloride, 100.35% and 0.27% for dextromethorphan hydrobromide respectively. Quantification of the components in syrup formulation was calculated against the peak areas of freshly prepared standard solutions. The method was validated as per ICH guidelines.

HPLC separation of antibiotics present in formulated and unformulated samples.

Analysis of antibiotics in formulated and unformulated samples demand a highly specific and rapid method as many antibiotics (e.g. beta-lactams) have serious stability problems. HPLC techniques can provide a valuable tool for generating highly pure preparations for characterizing the antimicrobial activities. In the present review article, column and mobile phase conditions for the various classes of antibiotics viz. penicillins, cephalosporins, macrolides, tetracyclines, aminoglycosides, quinolones, rifamycins etc. have been presented from April 1998 to November 2000. A brief discussion on chemical structure, spectrum of activity and action mechanism of each class has also been given.