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Developmental and photoregulation of al-1 and al-2, structural genes for two enzymes essential for carotenoid biosynthesis in Neurospora.

The levels of al-1 and al-2 transcripts change dramatically in response to light and development during the formation of Neurospora crassa asexual spores (conidia). al-1 and al-2 mRNAs accumulate throughout conidiation irrespective of lighting conditions initially at low levels. As conidiation proceeds, two increases in albino message accumulation are observed. This developmentally induced photoindependent message accumulation was not observed in Neurospora mutants blocked at relevant stages of conidiation. During conidiation, light induces additional accumulation of al-1 and al-2 gene-specific transcripts; the photoinduced increase in albino gene transcript levels was not observed in two Neurospora mutants, wc-1 and wc-2, that are defective in all physiological photoresponses.

Blotting, Northern↗

Theoretical and synthetic investigations of carbodiimide insertions into Al-CH3 and Al-N(CH3)2 bonds.

Carbodiimides are known to insert into aluminum-carbon bonds to form four-membered bidentate amidinate chelate rings. Insertions into Al-R and Al-NR'2 (R, R' = alkyl) have been reported in the literature. We have devised a mechanism for these insertions and modeled it using density functional theory (DFT) calculations. The calculated barrier heights for competitive insertions show the insertion into Al-N(CH3)2 goes through a lower barrier than the reaction with Al-CH3 for diisopropyl carbodiimide due to the necessity of forming a pentavalent carbon intermediate in the Al-CH3 case. However, insertion into Al-CH3 has the lower barrier for the reaction with di-tert-butyl carbodiimide because of steric effects, which is consistent with the published experimental results. We have synthesized aluminum amidinates containing two and three acetamidinate rings via insertion of 2 and 3 equiv of diisopropylcarbodiimide into trimethylaluminum (TMA). The crystal structure for [CH3C(N(i)Pr)2]2 AlCH3 is reported. We have found that, although the first insertion is rapid at room temperature, the second and third insertions require refluxing above 70 degrees C. We have calculated the barrier heights for the first and second insertion and have found that this is due to a higher barrier for the migration of the methyl group in the second insertion. This higher barrier is the result of the lack of an exergic precoordination of the carbodiimide to the metal center, which facilitates the first insertion.

Journal Article↗

Anionic and Neutral Aluminum Bis(N,N'-di-tert-butylethylenediamide) Complexes: [Al{[N(t-Bu)CH(2)](2)}(2)](-) and [Al{[N(t-Bu)CH(2)](2)}(2)](*).

The reaction of the aluminum triamide [{EtaN(t-Bu)CH(2)CH(2)N-t-Bu}Al{N(t-Bu)CH(2)}(2)] (1) with n-BuLi in hexane and diethyl ether gives the monomeric solvent-free lithium aluminum tetraamide [Li{N(t-Bu)CH(2)CH(2)N-t-Bu}(2)Al] (2), and the diethyl ether adduct [Et(2)O.Li{N(t-Bu)CH(2)CH(2)N-t-Bu}(2)Al] (3), respectively. The reaction of the diethyl ether adduct 3 with 2 equiv of the chelating nitrogen Lewis bases TMEDA ( identical withN,N,N',N'-tetramethylethylenediamine) and t-Bu(2)DAB ( identical withN,N'-di-tert-butyl-1,4-diazabutadiene) in diethyl ether affords the ionic complex [Li(TMEDA)(2)][Al{[N(t-Bu)CH(2)](2)}(2)] (4) and a mixture of the paramagnetic species [Li(t-BuDAB)(2)] and [Al{[N(t-Bu)CH(2)](2)}(2)], which cocrystallize 5, respectively. The reaction of the diethyl ether adduct 3 with 0.5 equiv of HgCl(2) yields the neutral paramagnetic species [Al{[N(t-Bu)CH(2)](2)}(2)] (6). Crystals of 2 are triclinic, of space group P&onemacr; (No. 2), with a = 15.894(5) Å, b = 15.473(5) Å, c = 9.975(3) Å, alpha = 93.74(2) degrees, beta = 91.97(2) degrees, gamma = 102.07(3) degrees, and Z = 4. Crystals of 3are monoclinic, of space group C2/c (No. 15), with a = 15.835(5) Å, b = 12.054(3) Å, c = 16.456(5) Å, beta = 111.56(3) degrees, and Z = 4. Crystals of 4are orthorhombic, of space group Pbca (No. 61), with a = 19.349(4) Å, b = 22.227(7) Å, c = 19.070(3) Å, and Z = 8. Crystals of 5 are orthorhombic, of space group Pmmn (No. 59), with a = 13.874(4) Å, b = 13.473(6) Å, c = 12.717(3) Å, and Z = 2. Crystals of 6 are monoclinic, of space group C2/c (No. 15), with a = 16.721(4) Å, b = 9.454(4) Å, c= 16.460(8) Å, beta = 113.27(3), and Z = 4.

Journal Article↗

Theoretical study of Al(n) and Al(n)O (n = 2-10) clusters.

The stable structures, energies, and electronic properties of neutral, cationic, and anionic clusters of Al(n) (n = 2-10) are studied systematically at the B3LYP/6-311G(2d) level. We find that our optimized structures of Al5(+), Al9(+), Al9(-), Al10, Al10(+), and Al10(-) clusters are more stable than the corresponding ones proposed in previous literature reports. For the studied neutral aluminum clusters, our results show that the stability has an odd/even alternation phenomenon. We also find that the Al3, Al7, Al7(+), and Al7(-) structures are more stable than their neighbors according to their binding energies. For Al7(+) with a special stability, the nucleus-independent chemical shifts and resonance energies are calculated to evaluate its aromaticity. In addition, we present results on hardness, ionization potential, and electron detachment energy. On the basis of the stable structures of the neutral Al(n) (n = 2-10) clusters, the Al(n)O (n = 2-10) clusters are further investigated at the B3LYP/6-311G(2d), and the lowest-energy structures are searched. The structures show that oxygen tends to either be absorbed at the surface of the aluminum clusters or be inserted between Al atoms to form an Al(n-1)OAl motif, of which the Al(n-1) part retains the stable structure of pure aluminum clusters.

Journal Article↗

Evaluation of AL-05712 and AL-05741 as thioltransferase mimics for the prevention and recovery of pre-cataractous changes in lens.

It has been previously shown that during the aging process, the human eye lens accumulates protein-glutathione mixed disulfides (PSSG) and that the reduced glutathione (GSH) level drops. These changes become even more pronounced during cataractogenesis. In this report, the ability of AL-05712 and AL-05741 to lower PSSG and elevate GSH in three separate model systems was evaluated. AL-05741 was able to decrease PSSG in the cell-free system by over 30% at a concentration of 0.1 mM. AL-05712, the ester form of AL-05741, decreased mixed disulfides by about 8% in the same system in the absence of any cellular esterases. Both compounds could partially inhibit the loss of GSH seen in the H2O2 control in cultured rat lenses and in addition, the accumulation of PSSG was substantially decreased. Human lenses incubated in AL-05712 showed a significant elevation of cortical GSH and a decrease in PSSG in three of four sets of cultured human lenses.

Animals↗

Spinobulbar muscular atrophy can mimic ALS: the importance of genetic testing in male patients with atypical ALS.

The clinical presentation of amyotrophic lateral sclerosis (ALS) is variable and overlaps with that of other motor neuron diseases such as spinobulbar muscular atrophy (SBMA; Kennedy disease). With the identification of disease-specific mutations such as the CAG repeat expansion in the androgen receptor in SBMA, an accurate molecular diagnosis can be made in some patients with motor neuron disease. To determine the extent of misdiagnosis of ALS we screened 147 male ALS patients and 100 unrelated male patients from 100 familial ALS (FALS) kindreds for the presence of the SBMA mutation using polymerase chain reaction methods. We show that ALS was clinically misdiagnosed in 2% of sporadic cases and in two of the 100 FALS kindreds. This study underscores the difficulty in distinguishing SBMA from ALS clinically, particularly in patients who lack the classic signs of each disease.

Amyotrophic Lateral Sclerosis↗

Preparation of ethereal oils (Al-Duhoun) by Ibn Al-Quff (13th century A.D.).

Ibn Al-Quff was born in Damascus. He learned medicine from Ibn Abi Usaibia. Ibn Al-Quff was excelled in medicine as well as in Surgery. He wrote several books, of which was "Al-Qumdah" (The Authority on Surgery). Another book was "Al-Shafi" (The Healer) on medicine. In the book "The Authority on Surgery", Ibn Al-Quff has devoted a special chapter, on the preparation of ethereal oils, which was commonly known as Al-Duhoun. He has described about 34 different oils together with their medical action.

Arab World↗

13C-(27)Al TRAPDOR and REDOR experiments for the detection of (13)C-(27)Al dipolar interactions in solids.

We report (13)C-(27)Al double resonance experiments (REDOR and TRAPDOR) on several aluminum organic compounds with the aim of detecting (13)C-(27)Al dipolar couplings and distances in solids. The (13)C and (27)Al pulses are applied to the same probe channel because their resonance frequencies are in close proximity. The different possibilities of controlling the efficiency of the TRAPDOR approach (by varying the (27)Al RF amplitude and the MAS frequency) are investigated. The results indicate that TRAPDOR is superior to REDOR in resolving differences in (13)C-(27)Al distances when choosing the proper experimental conditions. Where known, the crystal structure data are in qualitative agreement with the distance information extracted from our experiments. The experiment should be very valuable in different fields of solid state chemistry, where the interaction of organic and inorganic sample fractions is of fundamental importance.

Acetates↗

Three-dimensional through-bond homonuclear-heteronuclear correlation experiments for quadrupolar nuclei in solid-state NMR applied to (27)Al-O-(31)P-O-(27)Al networks.

We present here the first 3D homonuclear/heteronuclear correlation experiment applied to quadrupolar nuclei and making use of the sole scalar J-coupling. This experiment, based on the 2D-Homonuclear-Heteronuclear Single Quantum Correlation (H-HSQC) experiment, uses a relayed transfer from the (27)Al central transition to neighbouring (31)P spins and to the central transition of a second (27)Al. It confirms the correlation map characterizing the two (27)Al and the (31)P NMR signatures of (27)Al-O-(31)P-O-(27)Al chemically bonded molecular motifs.

Algorithms↗

Analysis of mutant quantity and quality in human-hamster hybrid AL and AL-179 cells exposed to 137Cs-gamma or HZE-Fe ions.

We measured the number of mutants and the kinds of mutations induced by 137Cs-gamma and by HZE-Fe (56Fe [600 MeV/amu, LET = 190 KeV/micrometer) in standard AL human hamster hybrid cells and in a new variant hybrid, AL-179. We found that HZE-Fe was more mutagenic than 137Cs-gamma per unit dose (about 1.6 fold), but was slightly less mutagenic per mean lethal dose, DO, at both the S1 and hprt- loci of AL cells. On the other hand, HZE-Fe induced about nine fold more complex S1- mutants than 137Cs-gamma rays, 28% vs 3%. 137Cs-gamma rays induced about twice as many S1- mutants and hprt-mutants in AL-179 as in AL cells, and about nine times more of the former were complex, and potentially unstable kinds of mutations.

Animals↗

Gd(1.33)Pt(3)(Al,Si)(8) and Gd(0.67)Pt(2)(Al,Si)(5): two structures containing a disordered Gd/Al layer grown in liquid aluminum.

Gd(1.33)Pt(3)Al(8) was synthesized by the combination of Gd and Pt in excess liquid aluminum. Addition of silicon resulted in the incorporation of a small amount of this element into the material to form the isostructural Gd(1.33)Pt(3)Al(7)Si. Both compounds grow as rodlike crystals with hexagonal cross section. The structures were refined in the rhombohedral space group R(-)3m, with cell parameters a = 4.3359(6) A and c = 38.702(8) A for the ternary and a = 4.3280(8) A and c = 38.62(1) A for the quaternary compound. The structure is comprised of stuffed arsenic-like PtAl(2) layers and disordered Gd/Al layers. Analysis of the hk0 zone reflections indicate the presence of an a = radical 3a supercell, but the structure is not ordered along c, as revealed by the highly diffuse reflections in the 0kl zone photos. Therefore, the compounds are disordered variants of the Gd(4)Pt(9)Al(24) type. Magnetic susceptibility studies reveal antiferromagnetic transitions at 15 K for the ternary and 7 K for the quaternary compound. Variation of the reactant ratio produces a different structure comprised of the same structural blocks, including the disordered Gd/Al layer. Gd(0.67)Pt(2)Al(5) and its quaternary analogue Gd(0.67)Pt(2)Al(4)Si form in the hexagonal system P6(3)/mmc with cell parameters a = 4.2907(3) A and c = 16.388(2) A for the ternary and a = 4.2485(6) A and c = 16.156(3) A for the quaternary compound.

Journal Article↗

Peculiar transformation of a nonaromatic Al(4)Cl(4)(NH(3))(4) into an aromatic Na(2)Al(4)Cl(4)(NH(3))(4).

We analyzed the molecular orbitals for a Al(4)Cl(4)(NH(3))(4) compound, which is a model of the (AlBr x NEt(3))(4) crystal structure recently reported by Schnöckel and co-workers. We found that even though Al(4)Cl(4)(NH(3))(4) contains a planar square Al(4) cluster it is not an aromatic compound. However, the addition of two sodium atoms to Al(4)Cl(4)(NH(3))(4) yields a new Na(2)Al(4)Cl(4)(NH(3))(4) compound which is a pi-aromatic molecule. We hope that prediction of this new compound will facilitate a synthesis of aluminum aromatic solids.

Journal Article↗

The adsorption of triethylenediamine on Al(2)O(3)-II: hydrogen bonding to Al-OH groups.

The hydrogen bonding of the triethylenediamine (TEDA) molecule to isolated Al-OH groups on partially dehydroxylated high area gamma-Al(2)O(3) powder has been studied using transmission IR spectroscopy. It has been found that TEDA adsorbs both singly and as multiple species to single Al-OH groups in clearly separable equilibrium stages of adsorption at 300 K. The reversible adsorption of a single TEDA molecule to Al-OH fits the Langmuir adsorption isotherm well, and the enthalpy of adsorption is found to be -15.6 +/- 0.5 kJ mol(-1) in the range of fractional coverage of 0.5-0.6. Red shifts of the Al-OH frequency from approximately -200 cm(-1) to approximately -1000 cm(-1) are observed as a result of -OH bonding to the N lone pair in the TEDA molecule.

Journal Article↗

Crime, hostility, wife battering, and the heart: on the Meehan et al. (2001) failure to replicate the Gottman et al. (1995) typology.

Comments on the J. C. Meehan, A. Holtzworth-Munroe, and K. Herron (2001) failure to replicate the J. M. Gottman et al. (1995) results of 2 different types of batterers, defined by heart rate reactivity: Type 1 men lowered their heart rate from baseline to the high-conflict marital discussion, and Type 2 men increased their heart rate from baseline to the high-conflict marital discussion. Discussion is about criminality-psychopathy literature associated hypoarousal and hyporeactivity and the hostility-cardiovascular disease literature, which reports associated hyperreactivity and hostility related to cardiovascular disease. The Type 1-Type 2 distinction should be referred to these two venerable literatures. This article proposes the hypothesis that the Meehan et al. study failed to replicate Gottman et al. because it used a low-conflict marital discussion rather than the high-conflict discussion Gottman et al. used. This article reviews a study that did use a high-conflict marital task and found results generally supporting the Gottman et al. findings.

Adult↗

Versailles minimal dataset for diagnosis of ALS: a distillate of the 2nd Consensus Conference on accelerating the diagnosis of ALS. Versailles 2nd Consensus Conference participants.

The 2nd Consensus Conference (Versailles) recommended that an ALS knowledge-base for initial healthcare providers, diagnosing neurologists and confirming neurologists should be defined to include a simplified version of diagnostic criteria less formal than the World Federation of Neurology El Escorial Revisted Criteria ('ALS diagnosis - An algorithm'), a set of rules concerning red flags which should increase the suspicion of ALS as the diagnosis and minimize the time between suspicion and referral for confirmation of diagnosis ('ALS axioms of referral'), as well as a site of symptom onset-specific checklist of minimal clinical examination, neuroimaging, electrodiagnostic, pulmonary function and laboratory test information required to confirm the diagnosis of ALS ('Versailles minimal dataset'). Although introductory discussions addressed the advantages and disadvantages of earlier diagnosis, false-positive or false-negative diagnosis, the frequency of follow-up and what potential biological markers to be followed, these issues will have to be further evaluated at future consensus conferences.

Diagnosis, Differential↗

The Neurophysiological Index in ALS.

The Neurophysiological Index (NI) consists of a mathematical derivation of three standardised neurophysiological measurements. Since these measurements are part of routine practice in any clinical neurophysiology laboratory, calculation of the NI is within the capability of any laboratory. The NI is derived from the CMAP, the DML and the F-wave frequency (CMAP amplitude/DML) x F frequency %), representing aspects of the effects of denervation and reinnervation, of degeneration of the terminal part of the motor axons, and of the excitability of anterior horn cells. We have shown that this simple index is reproducible in consecutive studies of normal subjects and of patients with ALS (intra-rater reliability), and is sensitive to change. In ALS, the NI differentiates rapidly and slowly progressive disease at least as sensitively as other measures in common use, including the ALS-FRS. We propose that the NI could be used as a sensitive measure of change during the course of ALS and its treatment. In combination with relevant measures of clinical benefit, such as ALS-FRS and a QoL measure, this could simplify trial design and allow more rapid determination of the efficacy of putative new therapies in clinical trials.

Amyotrophic Lateral Sclerosis↗

Effects of heat and electron irradiation on the melting behavior of Al-Si alloy particles and motion of the Al nanosphere within.

In situ heating and electron-beam irradiation in the transmission electron microscope were performed to study melting of Al-11.6 at.% Si alloy submicron particles supported on an amorphous-C thin film. It was found that electron irradiation could be used to melt the particles, even when the hot-stage specimen holder was kept at a much lower temperature than the bulk melting point (i.e. the eutectic temperature) of the particles. The critical current densities required to achieve partial melting increased linearly with the incident electron-beam energy for a given temperature. Comparison between this behavior and analytical calculations indicates that melting under electron-beam irradiation is caused by a temperature rise due to electron thermal spikes in the particles and poor thermal conduction away from the particles. The motion of the crystalline Al nanosphere inside the partially molten particles was also investigated, using the electron beam to both stimulate and observe the motion of the nanosphere. The irregular motion observed was quantified as antipersistent fractional Brownian motion. Analysis of possible phenomena contributing to the motion demonstrates that the incident electrons provide the fractional force that moves the Al nanosphere, and that gravity and the oxide shell on the partially molten particle cause the antipersistent behavior. Another interesting phenomenon observed in this study was that the crystalline Al nanosphere inside the partially molten Al-Si alloy particle followed a focused electron beam as it was moved about on the partially molten particle. This observation suggests that it may be possible to manipulate metallic nanospheres inside opaque liquids using an electron beam.

Journal Article↗

Protective roles of two aluminum (Al)-induced genes, HSP150 and SED1 of Saccharomyces cerevisiae, in Al and oxidative stresses.

We isolated two yeast cDNA clones whose transcripts are induced by aluminum (Al) metal stress. Partial nucleotide sequencing showed that one is the HSP150 gene encoding a secreted heat shock protein, and the other corresponds to the SED1 gene encoding a putative membrane protein. To clarify the biological functions of these genes, we analyzed the sensitivity of gene-disrupted mutants to Al stress and to oxidative stresses. The Al tests indicated that the HSP150 protein served a basal protective role in Al stress, but SED1 did not; both of the genes had protective roles for oxidative stresses. The results for the HSP150 gene suggest that there is an overlap between Al ion stress, oxidative stress and heat shock stress in yeast.

Aluminum↗