Organometallic Chemistry of Diphosphazanes. 11. Reactions of fac-[Mo(CO)3(MeCN){.eta.2-Ph2PN(Pri)PPh(DMP)}] (DMP = 3,5-Dimethyl-1-Pyrazolyl) with Diphosphazanes and Diphosphinoalkanes and Oxidative Addition with Iodine

The use of fac-[Mo(CO)(3)(MeCN)(eta(2)-L(1))] (1a) {L(1) = Ph(2)PN(Pr-i)PPh(DMP)}(2) as a precursor to metalloligands and bimetallic, heterotrimetallic, and heptacoordinated complexes is reported. The reaction of 1a with diphosphazane, dppa, or a diphosphinoalkane such as dppm or dppe yields the fac-eta(1)-diphosphine substituted metalloligands, fac-[Mo(CO)(3)(eta(2)-L(1))(eta(1)-PXP)] {PXP = dppa (2), dppm (3), and dppe (4)}. These undergo isomerization to yield the corresponding mer-diphosphine complexes (5-7). Oxidation of the uncoordinated phosphorus atom of the mer-eta(1)-dppm-substituted complex eventually provides mer-[Mo(CO)(3)-(eta(2)-L(1)){eta(1)-Ph(2)PCH(2)P(O)Ph(2)}](8). The structure of the latter complex has been confirmed by single crystal X-ray diffraction {triclinic system, P ($) over bar 1; a = 11.994(3), b = 14.807(2), c = 15.855(3) Angstrom; alpha = 114.24(1), beta = 91.35(2), and gamma = 98.95(1)degrees; Z = 2, 4014 data (F-0 > 5 sigma(F-0)), R = 0.066, R(W) = 0.069}. Treatment of the dppe metalloligand 7 with [PtCl2(COD)] yields the heterotrimetallic complex cis-[PtCl2{mer-[Mo(CO)(3)(eta(2)-L(1))(eta(1)-dppe]}(2)] (9). Attempts to prepare a related trimetallic complex with the dppm-containing metalloligand were unsuccessful; only the tetracarbonyl complex cis-[Mo(CO)(4)(eta(2)-L(1))] (1b) and cis-[PtCl2(eta(2)-dppm)] were obtained. Reaction of la with dppe in the ratio 2:1 yields the mer-mer dinuclear complex [{mer-[Mo(CO)(3)(eta(2)-L(1))]}(2)(mu-dppe)] (10) bridged by dppe. Oxidation of 1a with iodine yields the Mo(II) heptacoordinated complex [MoI2(CO)(2)(eta(3)-L(1))] (11) with tridentate PPN coordination. The same Mo(II) complex 11 is also obtained by the direct oxidation of the tetracarbonyl complex cis-[Mo(CO)(4)(eta(2)-L(1))] (1b) with iodine. The structure of 11 has been confirmed by X-ray diffraction studies {monoclinic system, Cc; a = 10.471(2), b = 19.305(3), c = 17.325(3) Angstrom; beta = 95.47(2)degrees; Z = 4, 3153 data (F-0 > 5 sigma(F-0)), R = 0.049, R(W) = 0.051}. This complex exhibits an unusual capped-trigonal prismatic geometry around the metal. A similar heptacoordinated complex 12 with a chiral diphosphazane ligand {L(3) = (S,R)-P(h)2PN-(*CHMePh)*PPh(DMP)} has also been synthesized.

Structural and optical properties of nonpolar (11-20) a-plane GaN grown on (1-102) r-plane sapphire substrate by plasma-assisted molecular beam epitaxy

We report the structural and optical properties of a-plane GaN film grown on r-plane sapphire substrate by plasma-assisted molecular beam epitaxy. High resolution X-ray diffraction was used to determine the out-of-plane and in-plane epitaxial relation of a-plane GaN to r-plane sapphire. Low-temperature photoluminescence emission was found to be dominated by basal stacking faults along with near-band emission. Raman spectroscopy shows that the a-GaN film is of reasonably good quality and compressively strained. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione

NaBH4 reduction of a cage dione proceeds in a stereospecific fashion to give the endo,endo-diol. This reactivity is related to the crystal structure.

OPSM - Opportunistic Power Save mode for Infrastructure IEEE 802.11 WLAN

We focus on the energy spent in radio communication by the stations (STAs) in an IEEE 802.11 infrastructure WLAN. All the STAs are engaged in web browsing, which is characterized by a short file downloads over TCP, with short duration of inactivity or think time in between two file downloads. Under this traffic, Static PSM (SPSM) performs better than CAM, since the STAs in SPSM can switch to low power state (sleep) during think times while in CAM they have to be in the active state all the time. In spite of this gain, performance of SPSM degrades due to congestion, as the number of STAs associated with the access point (AP) increases. To address this problem, we propose an algorithm, which we call opportunistic PSM (OPSM). We show through simulations that OPSM performs better than SPSM under the aforementioned TCP traffic. The performance gain achieved by OPSM over SPSM increases as the mean file size requested by the STAs or the number of STAs associated with the AP increases. We implemented OPSM in NS-2.33, and to compare the performance of OPSM and SPSM, we evaluate the number of file downloads that can be completed with a given battery capacity and the average time taken to download a file.

Experimental validation of analytical performance models for IEEE 802.11 networks

We consider the simplest IEEE 802.11 WLAN networks for which analytical models are available and seek to provide an experimental validation of these models. Our experiments include the following cases: (i) two nodes with saturated queues, sending fixed-length UDP packets to each other, and (ii) a TCP-controlled transfer between two nodes. Our experiments are based entirely on Aruba AP-70 access points operating under Linux. We report our observations on certain non-standard behavior of the devices. In cases where the devices adhere to the standards, we find that the results from the analytical models estimate the experimental data with a mean error of 3-5%.

Factors associated with 2009 pandemic influenza A (H1N1) vaccination acceptance among university students from India during the post-pandemic phase

Background: There was a low adherence to influenza A (H1N1) vaccination program among university students and health care workers during the pandemic influenza in many parts of the world. Vaccination of high risk individuals is one of the recommendations of World Health Organization during the post-pandemic period. It is not documented about the student's knowledge, attitude and willingness to accept H1N1 vaccination during the post-pandemic period. We aimed to analyze the student's knowledge, attitude and willingness to accept H1N1 vaccination during the post-pandemic period in India. Methods: Vaccine against H1N1 was made available to the students of Vellore Institute of Technology, India from September 2010. The data are based on a cross-sectional study conducted during October 2010 to January 2011 using a self-administered questionnaire with a representative sample of the student population (N = 802). Results: Of the 802 respondents, only 102/802 (12.7%) had been vaccinated and 105/802 (13%) planned to do so in the future, while 595/802 (74%) would probably or definitely not get vaccinated in the future. The highest coverage was among the female (65/102, 63.7%) and non-compliance was higher among men in the group (384/595; 64.5%) (p < 0.0001). The representation of students from school of Bio-sciences and Bio-technology among vaccinees is significantly higher than that of other schools. Majority of the study population from the three groups perceived vaccine against H1N1 as the effective preventive measure when compared to other preventive measures. 250/595 (42%) of the responders argued of not being in the risk group. The risk perception was significantly higher among female (p < 0.0001). With in the study group, 453/802 (56.4%) said that they got the information, mostly from media. Conclusions: Our study shows that the vaccination coverage among university students remains very low in the post-pandemic period and doubts about the safety and effectiveness of the vaccine are key elements in their rejection. Our results indicate a need to provide accessible information about the vaccine safety by scientific authorities and fill gaps and confusions in this regard.

Synthesis of new (Bi, La)(3)MSb(2)O(11) phases (M = Cr, Mn, Fe) with KSbO(3)-type structure and their magnetic and photocatalytic properties

Synthesis and structure of new (Bi, La)(3)MSb(2)O(11) phases (M = Cr, Mn, Fe) are reported in conjunction with their magnetic and photocatalytic properties. XRD refinements reflect that Bi(3)CrSb(2)O(11), Bi(2)LaCrSb(2)O(11), Bi(2)LaMnSb(2)O(11) and Bi(2)LaFeSb(2)O(11) adopt KSbO(3)-type structure (space group, Pn (3) over bar). The structure can be described through three interpenetrating networks where the first is the (M/Sb)O(6) octahedral network and other two are the identical networks having Bi(6)O(4) composition. The magnetic measurements on Bi(2)LaCrSb(2)O(11) and Bi(2)LaMnSb(2)O(11) show paramagnetic behaviour with magnetic moments close to the expected spin only magnetic moments of Cr(+3) and Mn(+3). The UV-Visible diffuse reflectance spectra are broad and indicate that these materials possess a bandgap of similar to 2 eV. The photocatalytic activity of these materials has been investigated by degrading Malachite Green (MG) under exposure to UV light.

An Empirical Analysis of Heterogeneity in IEEE 802.11 MAC Protocol Implementations and its Implications

Wireless LAN (WLAN) market consists of IEEE 802.11 MAC standard conformant devices (e.g., access points (APs), client adapters) from multiple vendors. Certain third party certifications such as those specified by the Wi-Fi alliance have been widely used by vendors to ensure basic conformance to the 802.11 standard, thus leading to the expectation that the available devices exhibit identical MAC level behavior. In this paper, however, we present what we believe to be the first ever set of experimental results that highlight the fact that WLAN devices from different vendors in the market can have heterogeneous MAC level behavior. Specifically, we demonstrate with examples and data that in certain cases, devices may not be conformant with the 802.11 standard while in other cases, they may differ in significant details that are not a part of mandatory specifications of the standard. We argue that heterogeneous MAC implementations can adversely impact WLAN operations leading to unfair bandwidth allocation, potential break-down of related MAC functionality and difficulties in provisioning the capacity of a WLAN. However, on the positive side, MAC level heterogeneity can be useful in applications such as vendor/model level device fingerprinting.

The Case for Non-Cooperative Multihoming of Users to Access Points in IEEE 802.11 WLANs

In many cases, a mobile user has the option of connecting to one of several IEEE 802.11 access points (APs),each using an independent channel. User throughput in each AP is determined by the number of other users as well as the frame size and physical rate being used. We consider the scenario where users could multihome, i.e., split their traffic amongst all the available APs, based on the throughput they obtain and the price charged. Thus, they are involved in a non-cooperative game with each other. We convert the problem into a fluid model and show that under a pricing scheme, which we call the cost price mechanism, the total system throughput is maximized,i.e., the system suffers no loss of efficiency due to selfish dynamics. We also study the case where the Internet Service Provider (ISP) could charge prices greater than that of the cost price mechanism. We show that even in this case multihoming outperforms unihoming, both in terms of throughput as well as profit to the ISP.

An analytical model for an IEEE~802.11 WLAN using DCF with two types of VoIP calls

In this paper we develop and numerically explore the modeling heuristic of using saturation attempt probabilities as state dependent attempt probabilities in an IEEE 802.11e infrastructure network carrying packet telephone calls and TCP controlled file downloads, using enhanced distributed channel access (EDCA). We build upon the fixed point analysis and performance insights. When there are a certain number of nodes of each class contending for the channel (i.e., have nonempty queues), then their attempt probabilities are taken to be those obtained from saturation analysis for that number of nodes. Then we model the system queue dynamics at the network nodes. With the proposed heuristic, the system evolution at channel slot boundaries becomes a Markov renewal process, and regenerative analysis yields the desired performance measures. The results obtained from this approach match well with ns2 simulations. We find that, with the default IEEE 802.11e EDCA parameters for AC 1 and AC 3, the voice call capacity decreases if even one file download is initiated by some station. Subsequently, reducing the voice calls increases the file download capacity almost linearly (by 1/3 Mbps per voice call for the 11 Mbps PHY)

Studies of phosphazenes .11. syntheses and structures of bis(primary amino)hexachlorocyclotetraphosphazenes and their dimethylamino derivatives

The bis(amino)hexachlorocyclotetraphosphazenes, 2-trans-6-N4P4 (NHR)2Cl6, R [dbnd] Me, Pr n Pr i , Bu n , CH2Ph, Ph, are obtained from the reaction of N4P4Cl8 with four mol. equivalents of the appropriate amine. Isomers with 2,4-structures have been isolated for R [dbnd] Bu n , CH2Ph. The 1H and 31P NMR spectra of these bis(amino) compounds and of their dimethylamino derivatives, 2-trans-6-N4P4 (NMe2)6 (NHR)2 are discussed.

Triclabendazole: An Intriguing Case of Co-existence of Conformational and Tautomeric Polymorphism

The crystal polymorphism of the anthelmintic drug, triclabendazole (TCB), is described. Two anhydrates (Forms I and II), three solvates, and an amorphous form have been previously mentioned. This study reports the crystal structures of Forms I (1) and II (2). These structures illustrate the uncommon phenomenon of tautomeric polymorphism. TCB exists as two tautomers A and B. Form I (Z'=2) is composed of two molecules of tautomer A while Form II (Z'=1) contains a 1:1 mixture of A and B. The polymorphs are also characterized by using other solid-state techniques (differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), PXRD, FT-IR, and NMR spectroscopy). Form I is the higher melting form (m.p.: 177 degrees C, Delta Hf=approximate to 105 +/- 4 Jg-1) and is the more stable form at room temperature. Form II is the lower melting polymorph (m.p.: 166 degrees C, Delta Hf=approximate to 86 +/- 3 Jg-1) and shows high kinetic stability on storage in comparison to the amorphous form but it transforms readily into Form I in a solution-mediated process. Crystal structure analysis of co-crystals 3-11 further confirms the existence of tautomeric polymorphism in TCB. In 3 and 11, tautomer A is present whereas in 4-10 the TCB molecule exists wholly as tautomer B. The DFT calculations suggest that the optimized tautomers A and B have nearly the same energies. Single point energy calculations reveal that tautomer A (in Form I) exists in two low-energy conformations, whereas in Form II both tautomers A and B exist in an unfavorable high-energy conformation, stabilized by a five-point dimer synthon. The structural and thermodynamic features of 1-11 are discussed in detail. Triclabendazole is an intriguing case in which tautomeric and conformational variations co-exist in the polymorphs.

Modeling of ternary solubilities of solids in supercritical carbon dioxide in the presence of cosolvents or cosolutes

The investigation of ternary solubilities of solids is essential for the efficient design of extraction processes. The ternary solubilities of solids for cosolvent and cosolute systems are complex functions of temperature, pressure and cosolvent/cosolute composition. The intermolecular interactions between the molecules have a significant role in the solubilities of mixed solids in SCCO2 and cosolvent ternary systems. Two model equations were developed for ternary SCCO2 + cosolvent/cosolute systems by using association and activity coefficient models. Both the model equations consist of five adjustable parameters and correlate the ternary solubilities of solids in terms of temperature, pressure, density and cosolvent/cosolute composition. The model equation for cosolvent systems correlated 43 solid pollutants-cosolvent-SCCO2, while the model equation for cosolute systems correlated 19 solute-cosolute-SCCO2 systems available in literature. The average AARD of the model equations are 4.73% and 4.87% for cosolvent ternary systems and mixed solids in SCCO2, respectively. (C) 2011 Elsevier B.V. All rights reserved.

A Rhodanine Derivative CCR-11 Inhibits Bacterial Proliferation by Inhibiting the Assembly and GTPase Activity of FtsZ

A perturbation of FtsZ assembly dynamics has been shown to inhibit bacterial cytokinesis. In this study, the antibacterial activity of 151 rhodanine compounds was assayed using Bacillus subtilis cells. Of 151 compounds, eight strongly inhibited bacterial proliferation at 2 mu M. Subsequently, we used the elongation of B. subtilis cells as a secondary screen to identify potential FtsZ-targeted antibacterial agents. We found that three compounds significantly increased bacterial cell length. One of the three compounds, namely, CCR-11 (E)-2-thioxo-5-({3-(trifluoromethyl)phenyl]furan-2-yl}methylene) thiazolidin-4-one], inhibited the assembly and GTPase activity of FtsZ in vitro. CCR-11 bound to FtsZ with a dissociation constant of 1.5 +/- 0.3 mu M. A docking analysis indicated that CCR-11 may bind to FtsZ in a cavity adjacent to the T7 loop and that short halogen oxygen, H-bonding, and hydrophobic interactions might be important for the binding of CCR-11 with FtsZ. CCR-11 inhibited the proliferation of B. subtilis cells with a half-maximal inhibitory concentration (IC50) of 1.2 +/- 0.2 mu M and a minimal inhibitory concentration of 3 mu M. It also potently inhibited proliferation of Mycobacterium smegmatis cells. Further, CCR-11 perturbed Z-ring formation in B. subtilis cells; however, it neither visibly affected nucleoid segregation nor altered the membrane integrity of the cells. CCR-11 inhibited HeLa cell proliferation with an IC50 value of 18.1 +/- 0.2,mu M (similar to 15 x IC50 of B. subtilis cell proliferation). The results suggested that CCR-11 inhibits bacterial cytokinesis by inhibiting FtsZ assembly, and it can be used as a lead molecule to develop FtsZ-targeted antibacterial agents.