Light-induced electron spin polarization in the ground state of water-soluble copper porphyrins

Light-induced spin-polarized transient EPR spectra are reported for several water-soluble copper porphyrins. The spectra are assigned to the doublet ground state, with emissive spin polarization resulting from photoexcitation and subsequent electronic relaxation. In contrast to other systems for which polarization of a doublet ground state has been observed, the exchange interactions in the copper porphyrins are strong and the geometry is fixed. It is proposed that intersystem crossing from the photoexcited trip-doublet to the trip-quartet state can lead to net polarization of the spin system and that this polarization is maintained during electronic decay, possibly via charge-transfer and exciplex states. The intensity of the observed spin polarization is essentially independent of the molecular orientation in the external field, but is strongly dependent on the nature of the charged peripheral groups. Possible reasons for this behavior are discussed.     

D-AKAP2, a novel protein kinase A anchoring protein with a putative RGS domain

Subcellular localization directed by specific A kinase anchoring proteins (AKAPs) is a mechanism for compartmentalization of cAMP-dependent protein kinase (PKA). Using a two-hybrid screen, a novel AKAP was isolated. Because it interacts with both the type I and type II regulatory subunits, it was defined as a dual specific AKAP or D-AKAP1. Here we report the cloning and characterization of another novel cDNA isolated from that screen. This new member of the D-AKAP family, D-AKAP2, also binds both types of regulatory subunits. A message of 5 kb pairs was detected for D-AKAP2 in all embryonic stages and in all adult tissues tested. In brain, skeletal muscle, kidney, and testis, a 10-kb mRNA was identified. In testis, several small mRNAs were observed. Therefore, D-AKAP2 represents a novel family of proteins. cDNA cloning from a mouse testis library identified the full length D-AKAP2. It is composed of 372 amino acids which includes the R binding fragment, residues 333-372, at its C-terminus. Based on coprecipitation assays, the R binding domain interacts with the N-terminal dimerization domain of RIalpha and RIIalpha. A putative RGS domain was identified near the N-terminal region of D-AKAP2. The presence of this domain raises the intriguing possibility that D-AKAP2 may interact with a Galpha protein thus providing a link between the signaling machinery at the plasma membrane and the downstream kinase.     

The apolipoprotein E allele epsilon 4 is overrepresented in patients with the Lewy body variant of Alzheimer's disease

We determined apolipoprotein E (ApoE) genotypes in 122 autopsied demented patients. The frequency of the ApoE epsilon 4 allele was 39.6% in Alzheimer's disease (AD), 29.0% in the Lewy body variant of AD (LBV), and 6.25% in diffuse Lewy body disease. For AD and LBV patients, the epsilon 4 frequency was significantly higher than that reported in nondemented controls (10 to 15%). Therefore, LBV and AD share ApoE epsilon 4 as a genetic risk factor, providing further evidence that these conditions overlap.     

Effects of citrate on the different phases of calcium oxalate crystallization

Urinary citrate appears to be an important factor in the crystallization process of calcium oxalate and calcium phosphate. The urinary excretion of citrate was found to be significantly lower in patients with calcium oxalate stone disease as compared with normal subjects, and about 30 per cent of the calcium stone formers can be considered as hypocitraturic. The lowest excretion of citrate was recorded in urine collected during the night. Citrate has significant effects on supersaturation with respect to both calcium oxalate and calcium phosphate, it also inhibits the growth of these crystals. In addition, citrate appears to be capable of inhibiting the aggregation of crystals composed of calcium oxalate, brushite, and hydroxyapatite. The heterogenous growth of calcium oxalate on calcium phosphate is also counteracted by citrate. As a consequence of the crucial role of citrate in these processes, stone prevention with alkaline citrate has become an attractive form of treatment in patients with recurrent stone formation. Single evening dose administration of sodium potassium citrate resulted in an of sodium potassium citrate resulted in an increased excretion of citrate, reduced levels of the calcium/citrate ratio as well as supersaturation with respect to calcium oxalate and a decreased rate of stone formation. However, conflicting results of stone preventive treatment with alkaline citrate have been reported by different groups, and long-term follow-up of patients treated in a randomized way is necessary to definitely assess the efficacy of alkaline citrate.     

International legislation on trace elements as contaminants in food: a review

Environmental contaminants such as trace elements may be present in all foods. Foods, raw materials and ingredients for food production are to an increasing extent traded across borders. Hence, there is a need for international legislation on trace elements as contaminants in food. In 1961, the FAO and WHO established the Codex Alimentarius to elaborate international food legislation. Contaminants in food are handled by the Codex Committee for Food Additives and Contaminants (CCFAC). The Codex Alimentarius system for developing legislation concerning trace elements as contaminants in food is based upon the Codex General Standard for Contaminants and Toxins in Food (GSCTF). By October 2001, the principles for setting maximum limits (MLs) for contaminants in food are agreed, and work is in progress on MLs for trace elements such as lead and cadmium in the various food categories. The status for the proposals is presented and discussed. The EU Regulation 466/2001 of 8 March 2001 sets MLs for lead and cadmium in various foods. This regulation will apply from 5 April 2002. The EU regulation is more detailed but similar to the Codex draft standards for lead and cadmium in food. In future, legislators and administrators in the Codex and EU and analytical chemists will discuss how to use more and better analytical data as risk-management tools to protect public health. Trace elements' speciation is an important aspect of this discussion.     

Intramolecular crosslinking of poly(vinyl alcohol)

Poly(vinyl alcohol) is crosslinked in dilute solution (c=0.1 wt%) with glutaraldehyde. The reaction product is characterized by viscometry and gel permeation chromatography (g.p.c.). The intrinsic viscosity decreases with increasing degree of crosslinking and does not depend on temperature. G.p.c. reveals that the reaction product is not homogeneous, but consists of a mixture of particles with different sizes, possibly both intra- and intermolecularly crosslinked molecules. The intramolecularly crosslinked molecules are smaller in size than the initial polymer molecules and their size depends on the degree of crosslinking. They possess a narrow particle size distribution even if the initial polymer sample had a broad molecular weight distribution.     

Miniature in vivo robots for remote and harsh environments

Long-term human space exploration will require contingencies for emergency medical procedures including some capability to perform surgery. The ability to perform minimally invasive surgery (MIS) would be an important capability. The use of small incisions reduces surgical risk, but also eliminates the ability of the surgeon to view and touch the surgical environment directly. Robotic surgery, or telerobotic surgery, may provide emergency surgical care in remote or harsh environments such as space flight, or extremely forward environments such as battlefields. However, because current surgical robots are large and require extensive support personnel, their implementation has remained limited in forward environments, and they would be difficult, or impossible, to use in space flight or on battlefields. This paper presents experimental analysis of miniature fixed-base and mobile in vivo robots to support MIS surgery in remote and harsh environments. The objective is to develop wireless imaging and task-assisting robots that can be placed inside the abdominal cavity during surgery. Such robots will provide surgical task assistance and enable an on-site or remote surgeon to view the surgical environment from multiple angles. This approach is applicable to long-duration space flight, battlefield situations, and for traditional medical centers and other remote surgical locations.     

Metabotropic glutamate receptors are involved in long-term potentiation in isolated slices of rat medial frontal cortex

The prelimbic region of medial frontal cortex in the rat receives a direct input from the hippocampus and this functional connection is essential for aspects of spatial memory. Activity-dependent changes in the effectiveness of synaptic transmission in the medial frontal cortex, namely long-term potentiation (LTP) and long-term depression (LTD) can persist for tens of minutes or hours and may be the basis of learning and memory storage. Glutamatergic activation of ionotropic receptors is required to induce both LTP and LTD. We now present evidence of the involvement of metabotropic glutamate receptors in LTP in isolated slices of frontal cortex. Repetitive bursts of stimulation at theta frequencies (TBS) were applied to layer II, and monosynaptic EPSPs were monitored in layer V neurons of the prelimbic area. TBS was found to be more effective at inducing LTP than tetanic stimulation at 100 Hz and produced LTP that lasted >30 min in 8 out of 14 neurons. Tetanic stimulation at 100 Hz in the presence of the N-methyl--aspartate (NMDA)-antagonist 2-amino-5-phosphonopentanoate (AP5) was reported to be a reliable method of inducing LTD in prelimbic cortex (). However we found that this protocol did not facilitate the induction of LTD. The role of metabotropic glutamate receptors (mGluR) in LTP was assessed by using the selective, broad-spectrum antagonist (R, S)-alpha-methyl-4- carboxyphenylglycine (MCPG). This drug significantly reduced the incidence of LTP after TBS to only 1 of 14 neurons (P < 0.02, chi2 test). The pooled responses to TBS in MCPG showed significantly reduced potentiation [(P < 0.02, analysis of variance (ANOVA)]. The broad-spectrum mGluR agonist (1S, 3R)-1-aminocyclopentane-1,3-dicarboxylic acid (ACPD) and the selective group I agonist S-3 hydroxyphenylglycine(S-3HPG) both produced membrane depolarization, an increase in number of spikes evoked by depolarizing current pulses, and a reduction in the afterhyperpolarization. Similar effects were produced by these agonists even when synaptic transmission was blocked by use of the gamma-aminobutyric acid-B (GABAB) receptor agonist, 200 microM baclofen, which suggests that group I mGluRs are present on layer V neurons. We conclude that mGluRs participate in the production of LTP in prelimbic cortex, and that this excitatory effect could be mediated by the postsynaptic group I mGluRs.     

Influence of age and health on immune functions and trace elements

Apparently healthy elderly donors were screened according to a simple protocol that included clinical examination and the determination of hematological and biochemical values. This screening was performed to detect subclinical alterations which might interfere with immune responses and trace element status. The elderly were divided into two groups. The first group consisted of 22 (age 76 +/- 1 years) positively selected elderly (PSE), i.e. healthy subjects with no hematological and laboratory alterations, the second one comprised 13 (age 75 +/- 1 years) negatively selected elderly (NSE). Data were then compared with those obtained from 40 (age 35 +/- 2 years) healthy young controls. In both groups of elderly donors, plasma zinc levels were normal, while plasma copper concentrations were increased. Intracellular values of zinc and copper in mono- and polymorphonuclear cells from both groups of elderly were within reference limits. After in vitro activation, granulocyte chemiluminescence activity was impaired only in NSE. A decrement in the number of circulating CD3 lymphocytes and an increase in CD8d, CD57 cells were found in PSE, while NSE showed an increased number of CD3,DR cells and CD8d, CD57, CD8b,CD57 and CD16,CD56 positive cells. Our results indicate that only plasma copper levels were affected by age, whereas subclinical alterations in hematological or biochemical values appear to impair immune responses in the elderly.