Joint Spatial Division and Multiplexing—The Large-Scale Array Regime

Adhikary, Ansuman,Junyoung Nam,Jae-Young Ahn,Caire, Giuseppe IEEE 2013 IEEE transactions on information theory Vol.59 No.10

<P>We propose joint spatial division and multiplexing (JSDM), an approach to multiuser MIMO downlink that exploits the structure of the correlation of the channel vectors in order to allow for a large number of antennas at the base station while requiring reduced-dimensional channel state information at the transmitter (CSIT). JSDM achieves significant savings both in the downlink training and in the CSIT uplink feedback, thus making the use of large antenna arrays at the base station potentially suitable also for frequency division duplexing (FDD) systems, for which uplink/downlink channel reciprocity cannot be exploited. In the proposed scheme, the multiuser MIMO downlink precoder is obtained by concatenating a prebeamforming matrix, which depends only on the channel second-order statistics, with a classical multiuser precoder, based on the instantaneous knowledge of the resulting reduced dimensional “effective” channel matrix. We prove a simple condition under which JSDM incurs no loss of optimality with respect to the full CSIT case. For linear uniformly spaced arrays, we show that such condition is approached in the large number of antennas limit. For this case, we use Szego's asymptotic theory of Toeplitz matrices to show that a DFT-based prebeamforming matrix is near-optimal, requiring only coarse information about the users angles of arrival and angular spread. Finally, we extend these ideas to the case of a 2-D base station antenna array, with 3-D beamforming, including multiple beams in the elevation angle direction. We provide guidelines for the prebeamforming optimization and calculate the system spectral efficiency under proportional fairness and max-min fairness criteria, showing extremely attractive performance. Our numerical results are obtained via asymptotic random matrix theory, avoiding lengthy Monte Carlo simulations and providing accurate results for realistic (finite) number of antennas and users.</P>

Modern Contraception and Anaemia Among Reproductive-age Women in India: Results From a Household Survey

Adhikary Mihir,Barman Poulami,Singh Bharti,Anand Abhishek 대한예방의학회 2024 예방의학회지 Vol.57 No.4

Objectives: Chronic anaemia is a significant health concern, particularly among women of childbearing age. Factors such as menstrual blood loss, childbirth, inadequate nutrition, closely spaced pregnancies, and recurrent gastrointestinal bleeding increase the risk of anaemia. This study investigated whether current contraceptive methods are associated with anaemia in Indian women of reproductive age.Methods: Cross-sectional data from the fifth round of the National Family Health Survey, conducted in 2019-2021, were used for this investigation. We included only non-pregnant and non-amenorrhoeic women in our analysis, resulting in a final analytical sample of 673 094 women aged 15-49. Bivariate cross-tabulations and multivariable logistic regression were employed to analyse the data.Results: The prevalence of anaemia was 57%, and the adjusted regression models found no significant association between the use of any contraceptive methods and women’s haemoglobin status. Women using traditional contraceptive methods had 1.08 (95% confidence interval, 1.05 to 1.11) times higher odds of having anaemia. Among the modern methods, other than injectables, all other methods—such as an intrauterine device, barrier use, and sterilisation—were associated with higher odds of anaemia compared to women who used contraceptive pills.Conclusions: This study explored the relationship between modern contraceptives and haemoglobin levels in India, revealing that injectables were associated with a notable reduction in the odds of anaemia, whereas traditional contraceptives and other modern methods exhibited positive associations with anaemia. These findings prompt policymakers to focus on anaemia reduction and safe contraceptives. More research is needed to inform decisions, given the scant literature.

Kinetics and Mechanism of the Pyridinolysis of Diethyl Isothiocyanophosphate in Acetonitrile

Adhikary, Keshab Kumar,Lee, Hai-Whang Korean Chemical Society 2012 Bulletin of the Korean Chemical Society Vol.33 No.3

The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of diethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit the two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with rate-limiting expulsion of the isothiocyanate leaving group from a trigonal bipyramidal pentacoordinated intermediate. The relatively large ${\beta}_x$ values with more basic and less basic pyridines imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb.

Kinetics and Mechanism of the Benzylaminolysis of O,O-Dimethyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

Adhikary, Keshab Kumar,Barai, Hasi Rani,Lee, Hai-Whang Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.12

Kinetic studies of the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots for substituent X variations in the nucleophiles are discrete with a break region between 4-Me and H, while the Hammett plots (log $k_2$ vs ${\sigma}_Z$) for substituent Z variations in the leaving groups are linear. The sign of the cross-interaction constant (${\rho}_{XZ}$) is positive for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ (= 2.54) value is observed with the weakly basic nucleophiles compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = 0.17). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a stepwise with a rate-limiting leaving group expulsion from the intermediate involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles.

Nucleophilic Substitution Reactions of N-Methyl α-Bromoacetanilides with Benzylamines in Dimethyl Sulfoxide

Adhikary, Keshab Kumar,Lee, Hai-Whang Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.3

Kinetic studies of the reactions of N-methyl-Y-${\alpha}$-bromoacetanilides with substituted X-benzylamines have been carried out in dimethyl sulfoxide at $25.0^{\circ}C$. The Hammett plots for substituent X variations in the nucleophiles (log $k_N$ vs ${\sigma}_X$) are slightly biphasic concave upwards/downwards, while the Bronsted plots (log $k_N$ vs $pK_a$) are biphasic concave downwards with breakpoints at X = H. The Hammett plots for substituent Y variations in the substrates (log $k_N$ vs ${\sigma}_Y$) are biphasic concave upwards/downwards with breakpoints at Y = H. The cross-interaction constant $\rho_{XY}$ values are all negative: $\rho_{XY}$ = -0.32 for X = Y = electron-donating; -0.22 for X = electron-withdrawing and Y = electron-donating; -1.80 for X = electron-donating and Y = electronwithdrawing; -1.43 for X = Y = electron-withdrawing substituents. Deuterated kinetic isotope effects are primary normal ($k_H/k_D$ > 1) for Y = electron-donating, while secondary inverse ($k_H/k_D$ < 1) for Y = electronwithdrawing substituent. The proposed mechanisms of the benzylaminolyses of N-methyl-Y-${\alpha}$-bromoacetanilides are a concerted mechanism with a five membered ring TS involving hydrogen bonding between hydrogen (deuterium) atom in N-H(D) and oxygen atom in C = O for Y = electron-donating, while a concerted mechanism with an enolate-like TS in which the nucleophile attacks the ${\alpha}$-carbon for Y = electronwithdrawing substituents.

Nucleophilic Substitution Reactions of α-Bromoacetanilides with Benzylamines

Adhikary, Keshab Kumar,Kim, Chan-Kyung,Lee, Bon-Su,Lee, Hai-Whang Korean Chemical Society 2008 Bulletin of the Korean Chemical Society Vol.29 No.1

Kinetic studies of the reactions of a-bromoacetanilides [YC6H4NHC(=O)CH2Br] with substituted benzylamines (XC6H4CH2NH2) have been carried out in dimethyl sulfoxide at 35.0 oC. The Hammett plots for substituent (Y) variations in the substrate (log kN vs. sY) are biphasic concave upwards/downwards with breaks at Y = 4-Cl (sY = 0.23). The Hammett coefficients rY and the cross-interaction constant rXY (= +0.16) are positive for sY 0.23, while the rY values are positive/negative [rY > 0 for X = (4-MeO and 4-Me) and rY < 0 for X = (H, 4-Cl and 3-Cl)] and the rXY (= -1.51) value is negative for sY ³ 0.23. Based on these and other results, the benzylaminolyses of a-bromoacetanilides are proposed to proceed through rate-limiting expulsion of the bromide leaving group from a zwitterionic tetrahedral intermediate, T, with a bridged transition state for s Y 0.23, while the reaction proceeds through concerted mechanism with an enolate-like TS in which the nucleophile attacks the a-carbon for s Y ³ 0.23.

Kinetics and Mechanism of the Pyridinolysis of Methyl Phenyl Phosphinic Chloride in Acetonitrile

Adhikary, Keshab Kumar,Lee, Hai-Whang Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.6

The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 $^{\circ}C$. The Hammett and Br${\o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive ${\rho}_X$ (= 2.94) and negative ${\beta}_X$ (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Br${\o}$nsted plots. Unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four $R_1R_2$P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of $k_H/k_D$ (= 2.10) involving deuterated anilines $[XC_6H_4NH_2(D_2)]$ for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.

Kinetics and Mechanism of the Benzylaminolysis of O,O-Diphenyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

Adhikary, Keshab Kumar,Lee, Hai-Whang Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.5

Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

Transition State Variation in the Anilinolysis of O-Aryl Phenyl Phosphonochloridothioates in Acetonitrile

Adhikary, Keshab Kumar,Lumbiny, Bilkis Jahan,Dey, Shuchismita,Lee, Hai-Whang Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.8

The nucleophilic substitution reactions of Y-O-aryl phenyl phosphonochloridothioates with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from an extremely large secondary inverse ($k_H/k_D$ = 0.439; min) to a primary normal ($k_H/k_D$ = 1.34; max) as both substituents of nucleophile (X) and substrate (Y) change from electron-donating to electron-withdrawing. These results are opposite to the DKIEs on Y-O-aryl methyl phosphonochloridothioates, and can be rationalized by the gradual transition state (TS) variation from backside to frontside attack. The trigonal bipyramidal pentacoordinate TS is proposed for a backside attack, while the hydrogen-bonded, four-center-type TS is proposed for a frontside attack. The negative values of the cross-interaction constants (${\rho}_{XY(H)}$ = -0.38 for $XC_6H_4NH_2$ and ${\rho}_{XY(D)}$ = -0.29 for $XC_6H_4ND_2$) indicate that the reactions proceed by a concerted $S_N2$ mechanism.

Significant Substituent Effects on Pyridinolysis of Aryl Ethyl Chlorophosphates in Acetonitrile

Adhikary, Keshab Kumar,Lee, Hai Whang Korean Chemical Society 2014 Bulletin of the Korean Chemical Society Vol.35 No.5

The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.