Ground and Excited State Intramolecular Proton Transfer in Salicylic Acid: an Ab Initio Electronic Structure Investigation

Energetics of the ground and excited state intramolecular proton transfer in salicylic acid have been studied by ab initio molecular orbital calculations using the 6-31G** basis set at the restricted Hartree-Fock (RHF) and configuration interaction-single excitation (CIS) levels and also using the semiempirical method AM1 at the RHF level as well as with single and pair doubles excitation configuration interaction spanning eight frontier orbitals (PECI = 8). The ab initio potential energy profile for intramolecular proton transfer in the ground state reveals a single minimum corresponding to the primary form, in the first excited singlet state, however, there are two minima corresponding to the primary and tautomeric forms, separated by a barrier of similar to 6 kcal/mol, thus accounting for dual emission in salicylic acid. Electron density changes with electronic excitation and tautomerism indicate no zwitterion formation. Changes in spectral characteristics with change in pH, due to protonation and deprotonation of salicylic acid, are also accounted for, qualitatively. Although the AM1 calculations suggest a substantial barrier for proton transfer in the ground as well as the first excited state of SA, it predicts the transition wavelength in near quantitative accord with the experimental results for salicylic acid and its protonated and deprotonated forms.

A parallel-serial binary arbitration scheme for collision-free multi-access techniques

Multi-access techniques are widely used in computer networking and distributed multiprocessor systems. On-the-fly arbitration schemes permit one of the many contenders to access the medium without collisions. Serial arbitration is cost effective but is slow and hence unsuitable for high-speed multiprocessor environments supporting very high data transfer rates. A fully parallel arbitration scheme takes less time but is not practically realisable for large numbers of contenders. In this paper, a generalised parallel-serial scheme is proposed which significantly reduces the arbitration time and is practically realisable.

Modeling Finite Buffer Effects on TCP Traffic over an IEEE 802.11 Infrastructure WLAN

The network scenario is that of an infrastructure IEEE 802.11 WLAN with a single AP with which several stations (STAs) are associated. The AP has a finite size buffer for storing packets. In this scenario, we consider TCP controlled upload and download file transfers between the STAs and a server on the wireline LAN (e.g., 100 Mbps Ethernet) to which the AP is connected. In such a situation, it is known (see, for example, (3), [9]) that because of packet loss due to finite buffers at the Ap, upload file transfers obtain larger throughputs than download transfers. We provide an analytical model for estimating the upload and download throughputs as a function of the buffer size at the AP. We provide models for the undelayed and delayed ACK cases for a TCP that performs loss recovery only by timeout, and also for TCP Reno.

State Dependent Attempt Rate Modeling of Single Cell IEEE 802.11 WLANs with Homogeneous Nodes and Poisson Arrivals

Analytical models of IEEE 802.11-based WLANs are invariably based on approximations, such as the well-known mean-field approximations proposed by Bianchi for saturated nodes. In this paper, we provide a new approach for modeling the situation when the nodes are not saturated. We study a State Dependent Attempt Rate (SDAR) approximation to model M queues (one queue per node) served by the CSMA/CA protocol as standardized in the IEEE 802.11 DCF. The approximation is that, when n of the M queues are non-empty, the attempt probability of the n non-empty nodes is given by the long-term attempt probability of n saturated nodes as provided by Bianchi's model. This yields a coupled queue system. When packets arrive to the M queues according to independent Poisson processes, we provide an exact model for the coupled queue system with SDAR service. The main contribution of this paper is to provide an analysis of the coupled queue process by studying a lower dimensional process and by introducing a certain conditional independence approximation. We show that the numerical results obtained from our finite buffer analysis are in excellent agreement with the corresponding results obtained from ns-2 simulations. We replace the CSMA/CA protocol as implemented in the ns-2 simulator with the SDAR service model to show that the SDAR approximation provides an accurate model for the CSMA/CA protocol. We also report the simulation speed-ups thus obtained by our model-based simulation.

Modeling finite buffer effects on TCP traffic over an IEEE 802.11 infrastructure WLAN

The network scenario is that of an infrastructure IEEE 802.11 WLAN with a single AP with which several stations (STAs) are associated. The AP has a finite size buffer for storing packets. In this scenario, we consider TCP-controlled upload and download file transfers between the STAs and a server on the wireline LAN (e.g., 100 Mbps Ethernet) to which the AP is connected. In such a situation, it is well known that because of packet losses due to finite buffers at the AP, upload file transfers obtain larger throughputs than download transfers. We provide an analytical model for estimating the upload and download throughputs as a function of the buffer size at the AP. We provide models for the undelayed and delayed ACK cases for a TCP that performs loss recovery only by timeout, and also for TCP Reno. The models are validated incomparison with NS2 simulations.

Tree 3-spanners in 2-sep chordal graphs: Characterization and algorithms

A spanning tree T of a graph G is said to be a tree t-spanner if the distance between any two vertices in T is at most t times their distance in G. A graph that has a tree t-spanner is called a tree t-spanner admissible graph. The problem of deciding whether a graph is tree t-spanner admissible is NP-complete for any fixed t >= 4 and is linearly solvable for t <= 2. The case t = 3 still remains open. A chordal graph is called a 2-sep chordal graph if all of its minimal a - b vertex separators for every pair of non-adjacent vertices a and b are of size two. It is known that not all 2-sep chordal graphs admit tree 3-spanners This paper presents a structural characterization and a linear time recognition algorithm of tree 3-spanner admissible 2-sep chordal graphs. Finally, a linear time algorithm to construct a tree 3-spanner of a tree 3-spanner admissible 2-sep chordal graph is proposed. (C) 2010 Elsevier B.V. All rights reserved.

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.

A template-free, combustion-chemical route to macroporous nickel monoliths displaying a hierarchy of pore sizes

Recently, we demonstrated a very general route to monolithic macroporous materials prepared without the use of templates (Rajamathi et al. J. Mater. Chem. 2001, 11, 2489). The route involves finding a precursor containing two metals, A and B, whose oxides are largely immiscible. Firing of the precursor followed by suitable sintering results in a monolith from which one of the oxide phases can be chemically leached out to yield a macroporous mass of the other oxide phase. The metals A and B that we employed in the demonstration were Ni and Zn. From the NiO-ZnO monolith that was obtained by decomposing the precursor, ZnO could be leached out at high pH to yield macroporous NiO. In the present work, we show that combustion-chemical (also called self-propagating) decomposition of a mixture of Ni and Zn nitrates with urea as a fuel yields an intimate mixture of the oxides that can be sintered and leached with alkali to form a macroporous NiO monolith. The new process that we present here thereby avoids the need for a crystalline single-source precursor. A novel and unanticipated aspect of the present work is that the combination of high temperatures and rapid quenching associated with combustion synthesis results in an intimate mixture of wurtzite ZnO and the metastable rock-salt Ni1-xZnxO where x is about 0.3. Leaching this monolith with alkali gives a macroporous mass of rock-salt Ni1-xZnxO, which upon reduction in H-2/Ar forms macroporous Ni and ZnO. There are thus two stages in the process that lead to two modes of pore formation. The first is associated with leaching of ZnO by alkali. The second is associated with the reduction of porous Ni1-xZnxO to give porous Ni and ZnO.

Analytical models for energy consumption in infrastructure WLAN STAs carrying TCP traffic

We develop analytical models for estimating the energy spent by stations (STAs) in infrastructure WLANs when performing TCP controlled file downloads. We focus on the energy spent in radio communication when the STAs are in the Continuously Active Mode (CAM), or in the static Power Save Mode (PSM). Our approach is to develop accurate models for obtaining the fraction of times the STA radios spend in idling, receiving and transmitting. We discuss two traffic models for each mode of operation: (i) each STA performs one large file download, and (ii) the STAs perform short file transfers. We evaluate the rate of STA energy expenditure with long file downloads, and show that static PSM is worse than just using CAM. For short file downloads we compute the number of file downloads that can be completed with given battery capacity, and show that PSM performs better than CAM for this case. We provide a validation of our analytical models using the NS-2 simulator.

Optimal crop planning and conjunctive use of water resources in a coastal river basin

Due to increasing trend of intensive rice cultivation in a coastal river basin, crop planning and groundwater management are imperative for the sustainable agriculture. For effective management, two models have been developed viz. groundwater balance model and optimum cropping and groundwater management model to determine optimum cropping pattern and groundwater allocation from private and government tubewells according to different soil types (saline and non-saline), type of agriculture (rainfed and irrigated) and seasons (monsoon and winter). A groundwater balance model has been developed considering mass balance approach. The components of the groundwater balance considered are recharge from rainfall, irrigated rice and non-rice fields, base flow from rivers and seepage flow from surface drains. In the second phase, a linear programming optimization model is developed for optimal cropping and groundwater management for maximizing the economic returns. The models developed were applied to a portion of coastal river basin in Orissa State, India and optimal cropping pattern for various scenarios of river flow and groundwater availability was obtained.

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.

State Dependent Attempt Rate modeling of single cell IEEE 802.11 WLANs with homogeneous nodes and Poisson packet arrivals

We study a State Dependent Attempt Rate (SDAR) approximation to model M queues (one queue per node) served by the Carrier Sense Multiple Access with Collision Avoidance (CSMA/CA) protocol as standardized in the IEEE 802.11 Distributed Coordination Function (DCF). The approximation is that, when n of the M queues are non-empty, the (transmission) attempt probability of each of the n non-empty nodes is given by the long-term (transmission) attempt probability of n saturated nodes. With the arrival of packets into the M queues according to independent Poisson processes, the SDAR approximation reduces a single cell with non-saturated nodes to a Markovian coupled queueing system. We provide a sufficient condition under which the joint queue length Markov chain is positive recurrent. For the symmetric case of equal arrival rates and finite and equal buffers, we develop an iterative method which leads to accurate predictions for important performance measures such as collision probability, throughput and mean packet delay. We replace the MAC layer with the SDAR model of contention by modifying the NS-2 source code pertaining to the MAC layer, keeping all other layers unchanged. By this model-based simulation technique at the MAC layer, we achieve speed-ups (w.r.t. MAC layer operations) up to 5.4. Through extensive model-based simulations and numerical results, we show that the SDAR model is an accurate model for the DCF MAC protocol in single cells. (C) 2012 Elsevier B.V. All rights reserved.

An Antitubulin Agent BCFMT Inhibits Proliferation of Cancer Cells and Induces Cell Death by Inhibiting Microtubule Dynamics

Using cell based screening assay, we identified a novel anti-tubulin agent (Z)-5-((5-(4-bromo-3-chlorophenyl)furan-2-yl)methylene)-2-thioxothiazoli din-4-one (BCFMT) that inhibited proliferation of human cervical carcinoma (HeLa) (IC50, 7.2 +/- 1.8 mu M), human breast adenocarcinoma (MCF-7) (IC50, 10.0 +/- 0.5 mu M), highly metastatic breast adenocarcinoma (MDA-MB-231) (IC50, 6.0 +/- 1 mu M), cisplatin-resistant human ovarian carcinoma (A2780-cis) (IC50, 5.8 +/- 0.3 mu M) and multi-drug resistant mouse mammary tumor (EMT6/AR1) (IC50, 6.5 +/- 1 mu M) cells. Using several complimentary strategies, BCFMT was found to inhibit cancer cell proliferation at G2/M phase of the cell cycle apparently by targeting microtubules. In addition, BCFMT strongly suppressed the dynamics of individual microtubules in live MCF-7 cells. At its half maximal proliferation inhibitory concentration (10 mu M), BCFMT reduced the rates of growing and shortening phases of microtubules in MCF-7 cells by 37 and 40%, respectively. Further, it increased the time microtubules spent in the pause (neither growing nor shortening detectably) state by 135% and reduced the dynamicity (dimer exchange per unit time) of microtubules by 70%. In vitro, BCFMT bound to tubulin with a dissociation constant of 8.3 +/- 1.8 mu M, inhibited tubulin assembly and suppressed GTPase activity of microtubules. BCFMT competitively inhibited the binding of BODIPY FL-vinblastine to tubulin with an inhibitory concentration (K-i) of 5.2 +/- 1.5 mu M suggesting that it binds to tubulin at the vinblastine site. In cultured cells, BCFMT-treatment depolymerized interphase microtubules, perturbed the spindle organization and accumulated checkpoint proteins (BubR1 and Mad2) at the kinetochores. BCFMT-treated MCF-7 cells showed enhanced nuclear accumulation of p53 and its downstream p21, which consequently activated apoptosis in these cells. The results suggested that BCFMT inhibits proliferation of several types of cancer cells including drug resistance cells by suppressing microtubule dynamics and indicated that the compound may have chemotherapeutic potential.

Complexity of distance paired-domination problem in graphs

Suppose G = (V, E) is a simple graph and k is a fixed positive integer. A subset D subset of V is a distance k-dominating set of G if for every u is an element of V. there exists a vertex v is an element of D such that d(G)(u, v) <= k, where d(G)(u, v) is the distance between u and v in G. A set D subset of V is a distance k-paired-dominating set of G if D is a distance k-dominating set and the induced subgraph GD] contains a perfect matching. Given a graph G = (V, E) and a fixed integer k > 0, the MIN DISTANCE k-PAIRED-DOM SET problem is to find a minimum cardinality distance k-paired-dominating set of G. In this paper, we show that the decision version of MIN DISTANCE k-PAIRED-DOM SET iS NP-complete for undirected path graphs. This strengthens the complexity of decision version Of MIN DISTANCE k-PAIRED-DOM SET problem in chordal graphs. We show that for a given graph G, unless NP subset of DTIME (n(0)((log) (log) (n)) MIN DISTANCE k-PAIRED-Dom SET problem cannot be approximated within a factor of (1 -epsilon ) In n for any epsilon > 0, where n is the number of vertices in G. We also show that MIN DISTANCE k-PAIRED-DOM SET problem is APX-complete for graphs with degree bounded by 3. On the positive side, we present a linear time algorithm to compute the minimum cardinality of a distance k-paired-dominating set of a strongly chordal graph G if a strong elimination ordering of G is provided. We show that for a given graph G, MIN DISTANCE k-PAIRED-DOM SET problem can be approximated with an approximation factor of 1 + In 2 + k . In(Delta(G)), where Delta(G) denotes the maximum degree of G. (C) 2012 Elsevier B.V All rights reserved.