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Direct observation of fine structure transitions in a paramagnetic nickel(II) complex using far-infrared magnetic spectroscopy: a new method for studying high-spin transition metal complexes.

Novel far-infrared (FIR) absorption spectroscopy in conjunction with multiple, fixed external magnetic fields (FIR magnetic spectroscopy, FIRMS) has been used to investigate pseudotetrahedral complexes with the formula M(PPh(3))(2)Cl(2) (M = Ni, Zn; Ph = C(6)H(5)). Crystal structures have been reported for the Ni complex; we report the structure of the Zn complex. Transmission spectra at 5 K of Ni(PPh(3))(2)Cl(2) (S = 1) at zero magnetic field exhibit absorption bands at 11.41, 15.28, and 23.0 cm(-1). The two lower frequency bands show great sensitivity to external magnetic field, and their field dependence is as expected for electron spin transitions allowing precise determination of the following parameters: |D| = 13.35(1) cm(-1), |E| = 1.93(1) cm(-1), g(x,y) = 2.20(1), g(z) = 2.00(1). Corresponding spectra of Zn(PPh(3))(2)Cl(2) (S = 0) exhibit bands only at >20 cm(-1), which show no field dependence. FIRMS is a promising technique for direct investigation of the electronic structure of high-spin transition metal complexes.

Journal Article↗

Analysis of Bonding and d-Electron Count in the Transition-Metal Carbides and Transition-Metal-Silicide Carbides with Discrete Linear M-C-M Units (M = Cr, Fe, Re) by Electronic Structure Calculations.

Electronic structures of the silicide carbides Tm(2)Fe(2)Si(2)C, Th(2)Re(2)Si(2)C, and ThFe(2)SiC and the carbide Ho(2)Cr(2)C(3) were calculated, using the extended Hückel tight binding method, to probe the d-electron counts of their transition metal atoms M (Cr, Fe, Re) the bonding of their linear M-C-M (M = Cr, Fe, Re) units. The nature of the short interlayer X.X (X = C, Si) bonds in Tm(2)Fe(2)Si(2)C, Th(2)Re(2)Si(2)C, and Ho(2)Cr(2)C(3) was also examined. Our study shows that the M-C bonds of the M-C-M units exist as double bonds. There is significant bonding in the interlayer Si.Si contacts of the silicide carbides R(2)M(2)Si(2)C (M = Fe, Re). The transition-metal atoms exist as d(10) ions in Tm(2)Fe(2)Si(2)C and Th(2)Re(2)Si(2)C. The d-electron count is slightly lower than d(10) in ThFe(2)SiC and close to d(5) in Ho(2)Cr(2)C(3).

Journal Article↗

Variations of transition zone volume and transition zone index after transurethral needle ablation for symptomatic benign prostatic hyperplasia.

BACKGROUND: Transurethral needle ablation (TUNA) is less invasive than other therapies for benign prostatic hyperplasia (BPH) and produces coagulative necrosis within selected adenoma lesions. The action mechanism of TUNA is still obscure, even though many early studies have demonstrated good clinical results of TUNA. It is of interest and importance to know how TUNA influences the volume of the intraprostatic region responsible for bladder outlet obstruction in order to elucidate the anatomical action mechanism of TUNA. METHODS: We retrospectively investigated postoperative variations in volumetric parameters of whole prostate volume (PV), transition zone volume (TZV) and transition zone index (TZI = TZV/PV) in 41 patients with symptomatic BPH who were treated with TUNA. The data were analyzed statistically in relation to the preoperative overall severity and postoperative therapeutic efficacy. RESULTS: Both PV and TZV showed a significant decrease at 3 months after TUNA (P < 0.01) as did the symptom score, quality of life (QOL) score and functional variables, and a decreased level of PV and TZV was sustained until 12 months of follow-up when compared to the baseline (P < 0.01 at 6 months, not significant at 12 months). TZI also showed a similar pattern with a significantly decreased level until the postoperative 6th month (P < 0.05 at 6 months, not significant at 12 months). In 'moderate' cases, TZI achieved the minimum value (0.44 +/- 0.13, P < 0.05 compared to the baseline) at 3 months of follow-up, but the level immediately increased, while in 'severe' cases, TZI gradually decreased and achieved the minimum value (0.44 +/- 0.08, P < 0.05 compared to the baseline) at 12 months of follow-up. In the evaluation by postoperative therapeutic efficacy, there were no significant differences in PV, TZV and TZI between 'excellent and good' cases (E/G group) and 'fair and poor/worse' cases (F/P group) at the baseline or 3 months of follow-up. Both of the efficacy groups showed a significant decrease in PV, TZV and TZI at 3 months when compared to the baseline (P < 0.05). The mean decrease in TZI was significantly larger in the E/G group than in the F/P group (0.064 +/- 0.13 vs 0.027 +/- 0.12, P < 0.05). CONCLUSION: Therapeutic efficacy of TUNA did not depend on the baseline value of PV, TZV and TZI, but on variation of a decrease in TZI during follow-up. Moreover, a slow and lasting decrease in TZI seemed to influence durability of the therapeutic efficacy of TUNA, which was clearly observed in 'severe' cases with a larger prostatic volume than in 'moderate' cases.

Aged↗

Understanding the nutrition transition: measuring rapid dietary changes in transitional countries.

OBJECTIVE: To understand methodological concerns related to dietary intake collection in transitional societies. DESIGN: Three days of household weighing and measurement of all food used and repeated 24-hour recalls. SETTING: Eight Chinese provinces. SUBJECTS: Five thousand nine hundred and fifty-two and 5152 adults aged 20-45 years in 1989 and 1997, respectively. RESULTS: Great variance exists in the types and quantity of animal products used in common recipes. For example, the proportion of pork from lean cuts in 'stir-fried fresh pepper and pork' varies between 14 and 24% in urban and rural areas and the total pork content for 100 g (dish) varies by 15 to 19 g between rural and urban areas in each of eight provinces. Another challenge relates to the variation in the edible vegetable oil content added during food preparation. Reliance on standard recipes for each fried dish would miss the variations in oil use over time, space and socio-economic status. CONCLUSIONS: Dietary change is rapid in transitional countries. Reliance on recipes standardised for animal food and edible oil contents will lead to very large systematic errors in the measurement of energy, fat and protein intakes.

Adult↗

The nutrition and health transition in the North West Province of South Africa: a review of the THUSA (Transition and Health during Urbanisation of South Africans) study.

OBJECTIVE: To describe how urbanisation influences the nutrition and health transition in South Africa by using data from the THUSA (Transition and Health during Urbanisation of South Africans) study. DESIGN: The THUSA study was a cross-sectional, comparative, population-based survey. SETTING: The North West Province of South Africa. SUBJECTS: In total, 1854 apparently healthy volunteers, men and women aged 15 years and older, from 37 randomly selected sites. Pregnant and lactating women, those with diagnosed chronic diseases and taking medication, with acute infections or inebriated were excluded but screened for hypertension and diabetes mellitus. Subjects were stratified into five groups representing different levels of urbanisation in rural and urban areas: namely, deep rural, farms, squatter camps, townships and towns/cities. OUTCOME MEASURES AND METHODS: Socio-economic and education profiles, dietary patterns, nutrient intakes, anthropometric and biochemical nutrition status, physical and mental health indicators, and risk factors for non-communicable diseases (NCDs) were measured using questionnaires developed or adapted and validated for this population, as well as appropriate, standardised methods for the biochemical analyses of biological samples. RESULTS: Subjects from the rural groups had lower household incomes, less formal education, were shorter and had lower body mass indices than those in the urban groups. Urban subjects consumed less maize porridge but more fruits, vegetables, animal-derived foods and fats and oils than rural subjects. Comparing women from rural group 1 with the urban group 5, the following shifts in nutrient intakes were observed: % energy from carbohydrates, 67.4 to 57.3; from fats, 23.6 to 31.8; from protein, 11.4 to 13.4 (with an increase in animal protein from 22.2 to 42.6 g day(-1)); dietary fibre, 15.8 to 17.7 g day(-1); calcium, 348 to 512 mg day(-1); iron from 8.4 to 10.4 mg day(-1); vitamin A from 573 to 1246 mug retinol equivalents day(-1); and ascorbic acid from 30 to 83 mg day(-1). Serum total cholesterol, low-density lipoprotein cholesterol and plasma fibrinogen increased significantly across groups; systolic blood pressure >140 mmHg was observed in 10.4-34.8% of subjects in different groups and diabetes mellitus in 0.8-6.0% of subjects. Women in groups 1 to 5 had overweight plus obesity rates of 48, 53, 47, 61 and 61%, showing an increase with urbanisation. Subjects from group 2 (farm dwellers) showed the highest scores of psychopathology and the lowest scores of psychological well-being. The same subjects consistently showed the lowest nutrition status. CONCLUSIONS: Urbanisation of Africans in the North West Province is accompanied by an improvement in micronutrient intakes and status, but also by increases in overweight, obesity and several risk factors for NCDs. It is recommended that intervention programmes to promote nutritional health should aim to improve micronutrient status further without leading to obesity. The role of psychological strengths in preventing the adverse effects of urbanisation on health needs to be examined in more detail.

Adolescent↗

Nucleoprotein transitions during spermiogenesis in mice with transition nuclear protein Tnp1 and Tnp2 mutations.

Chromatin remodeling during spermiogenesis is characterized by a series of nuclear protein replacements. Histones are replaced by transition nuclear proteins, which are in turn replaced by protamines. The transition nuclear proteins, TP1 and TP2, and the protamines, PRM1 and PRM2, are the major nuclear proteins involved in this process. Biochemical studies of mice with null mutations in one of the Tnp genes showed that the absence of one TP led to an apparent elevation in the amount of the remaining TP in the testis. To investigate the mechanism of changes of protein levels and effects of one Tnp mutation on other nuclear proteins, we used immunohistochemistry techniques to determine the distribution of these nuclear proteins. In contrast to previous biochemical analyses, which indicated that nuclear protein replacement was sequential with little overlap between the protein types, we found considerable overlap in the nucleoprotein types during spermiogenesis. The TPs, which appear in the nucleus before histone displacement is complete, were shared among genetically inequivalent spermatids. The absence of one TP did not affect the time of appearance of the other TP or of the protamines, but it did affect the displacement of the other TP, leading to its abnormal retention in the nucleus. The elevated levels of the remaining TP in Tnp-mutant mice appeared to be a consequence of the prolonged retention, rather than increased synthesis. Thus the absence of one of the TPs did not significantly affect transcription or translation of the other basic proteins, but it did affect posttranslational events.

Animals↗

First-order Fréedericksz transition above the nematic-smectic-a phase transition.

The Fréedericksz transition is investigated for thin homeotropic cells of a negative dielectric anisotropy liquid crystal above its nematic-smectic-A phase transition temperature in a spatially uniform electric field. For very thin cells, a crossover from second- to first-order Fréedericksz behavior is observed; no additional fields are necessary. The results are consistent with the theory of Shi [Liq. Cryst. 29, 121 (2002)]].

Journal Article↗

Surface ordering transitions at a liquid crystal-solid interface above the isotropic smectic-A transition.

The degree of orientational order induced by confining cylindrical surfaces is monitored via deuteron nuclear magnetic resonance linesplitting and linewidth above the smectic-A to isotropic phase transition. The orientational order strongly depends on the length of the surfactant coupling molecule, on the surface coverage, and on the liquid crystal. Continuous and stepwise growth of orientational order and surface-induced orientational order transitions found in the isotropic phase are explained in terms of a simplified model of surface-induced layering and molecular self-diffusion.

Journal Article↗

Dewetting near the glass transition: transition from a capillary force dominated to a dissipation dominated regime.

Dynamics and corresponding morphology of dewetting of thin polystyrene films at temperatures close to the glass transition were investigated by measuring simultaneously dewetted distance and width of the rim. Comparing the opening of cylindrical holes with the retraction of a straight contact line revealed (i). a drastic influence of the geometry (planar or radial symmetry) on the dynamics at early stages, (ii). a new logarithmic dewetting regime, and (iii). transitions between four dewetting regimes clearly indicated by changes in the shape of the rim. The complete dewetting scenario can be understood as an initial dominance of capillary driving forces, which is progressively overtaken by dissipation related to the increasing size of the rim.

Journal Article↗

Two-dimensional metal-insulator transition as a percolation transition in a high-mobility electron system.

By carefully analyzing the low temperature density dependence of 2D conductivity in undoped high-mobility n-GaAs heterostructures, we conclude that the 2D metal-insulator transition in this 2D electron system is a density inhomogeneity driven percolation transition due to the breakdown of screening in the random charged impurity disorder background. In particular, our measured conductivity exponent of approximately 1.4 approaches the 2D percolation exponent value of 4/3 at low temperatures and our experimental data are inconsistent with there being a zero-temperature quantum critical point in our system.

Journal Article↗

Universal transition state for high-pressure zinc blende to rocksalt phase transitions.

First-principles density functional calculations show that the high-pressure transitions of different semiconductors from zinc blende to rocksalt go through a transition state, which is universal in the sense that its position along the path and the corresponding geometry is independent of the chemical components of the semiconductor. This is explained using a Landau-like model expansion of the free energy in cosine functions of atomic position.

Journal Article↗

Extent and nature of transitions of route among heroin addicts in treatment--preliminary data from the Drug Transitions Study.

Preliminary data are presented here from a study of drug transitions in the UK. These support the contention that differences in route of administration are likely to be reflected in differing patterns of drug use, and associated with differing health risks for the individual drug user. Heroin 'chasers' were found to have robust and long-term patterns of heroin use and could not merely be considered as pre-injectors. They were also younger. No differences were found in the typical daily doses prior to entering treatment between chasers and injectors. Subjects who usually 'chased the dragon' but who would also inject were less likely to have shared injecting equipment in the past. Transitions between different routes of use were found in most directions. However, changes from 'chasing' to injection were most common. Year of initiation into heroin use was also related to initial route of use.

Drug Administration Routes↗

Invasion and metastasis in colorectal cancer: epithelial-mesenchymal transition, mesenchymal-epithelial transition, stem cells and beta-catenin.

Invasion by colorectal carcinomas is characterized by an epithelial-mesenchymal transition (EMT)-like dedifferentiation of the tumor cells. However, a redifferentiation towards an epithelial phenotype, resembling a mesenchymal-epithelial transition, is detectable in metastases. This indicates that malignant progression is based on dynamic processes, which cannot be explained solely by irreversible genetic alterations, but must be additionally regulated by the tumor environment. The main oncoprotein in colorectal cancer is the Wnt pathway effector beta-catenin, which is overexpressed due to mutations in the APC tumor suppressor in most cases. EMT of the tumor cells is associated with a nuclear accumulation of the transcriptional activator beta-catenin, which is reversed in metastases. Nuclear beta-catenin is involved in two fundamental processes in embryonic development: EMT and stem cell formation. Accumulating data demonstrate that aberrant nuclear expression of beta-catenin can also confer these two abilities to tumor cells, thereby driving malignant tumor progression.

Cell Nucleus↗

Transition to living: the neglected component of transition programming for individuals with learning disabilities.

The purpose of this article is to document the need for assisting individuals with learning disabilities (LD) to transition to adult life, with particular emphasis on aspects of adult life other than employment and postsecondary education. The adult roles emphasized are maintaining a home, becoming appropriately involved in the community (including recreation and leisure activities), and experiencing satisfactory personal and social relationships. The first section of this article reviews the results of major studies on the adult adjustment of individuals with LD, and discusses these individuals' learning characteristics. The second component briefly highlights existing models of career education and life skills education. The third section focuses on current practices in programming for adolescents with LD; and the final section proposes steps that must be taken if we are to more effectively help these individuals in their transition to all aspects of adult life.

Adolescent↗

Sodium dodecyl sulfate-bovine plasma albumin complex. Structural transition from native to relatively compact globule forms with mobile side chains in acidic region--N-F transition.

The acid-induced isomerization (the N-F transition) and expansion of sodium dodecyl sulfate-bovine plasma albumin complex (ADm; m, molar ratio of added sodium dodecyl sulfate to bovine plasma albumin; O less than or equal to m less than or equal to 12) were studied by measuring CD-resolved secondary structure, fluorescence polarization and life-time of tryptophyl fluorophors, acid-titration with the electrostatic correction for the surface potential, 1H-n.m.r. spectra and cross relaxation time between irradiated and observed protons. The immobilization of tryptophyl fluorophors observed in the F-form of AD0 was suppressed in the F-form of AD10. The acidtitration analysis of AD12 showed non salt-bonding between carboxylate groups and cationic side chains in the F-form, as in the case of AD0, indicating charged side chains being presumably mobile. 1H-n.m.r. spectra and cross relaxation times between irradiated and observed protons in the F-form of AD10 indicated the increase in the local motion. On the other hand, AD10 and AD12 did not show any significant change in the CD-resolved secondary structure in the N-F transition region. The F-form of AD10 or AD12 may therefore be the moltenglobule state which has secondary structure similar to the N-form of the complexes with fluctuating tertiary structure (side chains).

Animals↗

Transitional cell carcinoma of the renal pelvis with choriocarcinomatous differentiation. Immunohistochemical and immunoelectron microscopic assessment of human chorionic gonadotropin production by transitional cell carcinoma of the urinary bladder.

BACKGROUND: There have been 12 documented cases of choriocarcinoma arising in the urinary bladder, either alone or in combination with other epithelial tumors. It has been shown that some high-grade transitional cell carcinomas (TCC), without obvious syncytiotrophoblastic elements, can produce human chorionic gonadotrophins (HCG). METHODS: A case of choriocarcinoma, in association with high-grade TCC of the renal pelvis, was encountered in an 80-year-old man. For additional evaluation of HCG production by TCC, 25 consecutive cases of invasive high-grade TCC of the bladder were stained with an anti-HCG antibody. Immunogold staining also was performed in two of the cases studied. RESULTS: Immunoperoxidase staining of the renal pelvis tumor showed focal positivity for HCG within the TCC and a more intense reaction as the tumor cells differentiated into choriocarcinoma elements. Seven of the 25 cases (28%) displayed varying degrees of reactivity within individual cells or groups of cells. In an additional case, typical syncytiotrophoblastic giant cells without cytotrophoblasts were seen in a high-grade TCC. Immunogold studies demonstrated positive labeling in the cytoplasm of carcinoma cells in a case of TCC without syncytiotrophoblasts and in the syncytiotrophoblastic giant cells in the one case in which these were present. CONCLUSIONS: The findings support a metaplastic origin of cases of choriocarcinoma arising primarily in the urothelial tract.

Aged↗

Changes of phenotypic expression of prostatic antigen in secondary transitional cell carcinoma of the prostate: evidence for induction phenomenon as a mechanism for acquisition of prostatic antigens in prostatic transitional cell carcinoma.

BACKGROUND: In vitro and experimental studies of mesenchymal-epithelial interaction for the prostatic stroma have demonstrated that the prostatic stroma is capable of inducing the nonprostatic epithelium to acquire many features of prostatic epithelium. We investigated whether this phenomenon could be observed in vivo in human prostatic stroma. MATERIALS AND METHODS Sixty transitional cell carcinoma (TCC) of the urinary bladder: (a) 20 with glandular lumen; (b) 20 without glandular lumen: (c) 10 mixed TCC-adenocarcinoma (ACA); and (d) 10 with synchronous or metachronous TCC of the prostate; and three primary TCC of the prostate were examined and submitted for immunostaining for prostatic acid phosphatase (PAP) and prostatic specific antigen (PSA). RESULTS: There was a spectrum of immunostaining for PSA ranging from negative reactivity in TCC without glandular lumen of the urinary bladder, to focal and weak reactivity in single cells with varying degrees of nonmucinous glandular differentiation and to strong reactivity in groups of cells in primary and synchronous or metachronous TCC in the prostate. The areas of carcinoma geographically closest to the prostate and with the most extensive nonmucinous glandular differentiation displayed the most frequent and strongest immunoreactivity for PSA. The immunoreactivity for PAP was usually stronger than for PSA. Four cases of TCC and mixed TCC-ACA were immunoreactive only for PAP. Furthermore, there was a change in the phenotype of TCC in the urinary bladder as it spread into the prostate. For 10 TCC in the urinary bladder with synchronous or metachronous tumor in the prostate, all TCC in the urinary bladder were negative for PAP and PSA, whereas six TCC in the prostate were focally positive. CONCLUSIONS: The spectrum of immunoreactivity for PAP and PSA and the change in immunoreactivity of TCC of the urinary bladder as it spreads into the prostate are likely induced by the prostatic stroma through the mechanism of mesenchymal-epithelial interaction. Prostate 47:172-182, 2001.

Acid Phosphatase↗