A Theoretical Study of the Interaction Between Cytosine and BX<Subscript>3</Subscript> (X = F,Cl) Systems

The B3LYP method of DFT and HF theories of ab initio with 6-311+G^** basis sets were used to predict the geometries of the cytosine-BX₃ (X,=F, Cl) complex systems. Four conformers were obtained with no imaginary frequencies, respectively. The binding energies, enthalpies and Gibbs energies of cytosine-BX₃ have been obtained. The analyses of the combinations between cytosine and BX₃ using the natural bond orbital (NBO) method and thermodynamics indicate that the complexes (a) and (e), which depend on the proton affinities of the oxygen on the cytosine and boron in BX₃, are the most stable ones with their combination energies of −234.21 and −228.23 kJ.mol⁻¹ (B3LYP method, BSSE corrected). Based on the calculation results, a reasonable method was employed to calculate the change in the enthalpies and Gibbs energies to form eight complexes in the gaseous state at 298.15K and 101.325 kPa. It can be shown that the conformers (a) and (e) are the most stable and form readily.     

New compounds via Mannich reaction of cytosine, paraformaldehyde and cyclic secondary amines

The Mannich reaction of cytosine, paraformaldehyde and cyclic secondary amines in the presence of acetic acid gives 5-(4′-morpholinyl)methylcytosine, 5-(1′-piperidinyl)methylcytosine, 5-(1′-pyrrolidinyl)methylcytosine, 5-(4′-methyl-1′-piperidinyl)methylcytosine, 5-(3′-methyl-1′-piperidinyl)methylcytosine and 5-(2′-methyl-1′-piperidinyl)methylcytosine. These products are quite different from those obtained via cytosine aminomethylation previously described in the literature.     

半波片角度失配对通道调制型偏振成像效果的影响及补偿

通道调制型偏振成像系统能够实时地对目标进行全偏振成像,是当前偏振成像领域的研究热点之一.基于萨瓦板的通道调制型偏振仪中半波片的光轴方向对成像结果的准确性有较大的影响.本文分析了半波片失配角的大小对探测器采集到的光强分布的影响,得到了二者之间的表达式,根据该表达式提出通过测量半波片失配角对系统进行定标并利用测得的半波片失配角对偏振成像的解调结果进行修正和补偿的方法.计算机仿真结果显示失配角为0.5?时,S1,S2和S3的解调结果准确度在经过修正补偿后分别提高了0.06%,3.49%和3.49%.表明该方法能够较好地对解调出的偏振斯托克斯参数图像进行补偿,得到更精确的成像结果,对提高通道调制型偏振成像的质量具有重要的意义.     

失配情况下匹配模处理的仿真研究*

匹配场处理是一种水声学和物理学相结合的信号处理技术,其在水下目标定位方面的高精度特点使得该方法受到广泛关注。匹配模处理是工作在模态空间的匹配处理方法。相对于匹配场处理方法,匹配模处理方法只处理声场中有关声源位置信息的数据(然而匹配场处理方法使用了全部声场数据),这样就可以减小环境失配对定位的影响。本文研究了在环境发生失配时,通过选取受失配影响较小的模态组合,得出的定位结果更加精确。     

Design of allele-specific primers and detection of the human ABO genotyping to avoid the pseudopositive problem

PCR experiments using DNA primers forming mismatch pairing with template lambda DNA at the 3' end were carried out in order to develop allele-specific primers capable of detecting SNP in genomes without generating pseudopositive amplification products, and thus avoiding the so-called pseudopositive problem. Detectable amounts of PCR products were obtained when primers forming a single or two mismatch pairings at the 3' end were used. In particular, 3' terminal A/C or T/C (primer/template) mismatches tended to allow PCR amplification to proceed, resulting in pseudopositive results in many cases. While less PCR product was observed for primers forming three terminal mismatch pairings, target DNA sequences were efficiently amplified by primers forming two mismatch pairings next to the terminal G/C base pairing. These results indicate that selecting a primer having a 3' terminal nucleotide that recognizes the SNP nucleotide and the next two nucleotides that form mismatch pairings with the template sequence can be used as an allele-specific primer that eliminates the pseudopositive problem. Trials with the human ABO genes demonstrated that this primer design is also useful for detecting a single base pair difference in gene sequences with a signal-to-noise ratio of at least 45.     

“Orthogonalized” sparsity enhanced mismatch models for wireless heterogeneous networks

Performance of MIMO precoder for heterogeneous networks can be hindered by a lack of accurate channel state information. The sparsity enhanced mismatch model (SEMM) has been proposed recently to account for the channel estimate mismatch problem by exploiting the inherent sparse characteristics of MIMO interference channels. When (single user-MIMO) SU-MIMO precoder design takes into account the SEMM, it was shown to have better transmission performance compared to the conventional norm ball mismatch model (NBMM) in a single-user multi-victims scenario. However, when communicating and interference channels are highly correlated, which can happen frequently in ultra-dense heterogeneous networks, performance of the SEMM precoder degrades and in some cases, underperforms the NBMM precoder. An “orthogonalized” SEMM (OSEMM) is proposed herein to modify the SEMM such that it is better suited for correlated channels. The concept of orthogonalization of channels is not new but this work uses it to enhance the SEMM, which creates synergy between transmission performance and robustness toward channel mismatch error. Two variants of the OSEMM are proposed, namely the OSEMM-LQ and OSEMM-SVD, to modify the basis expansion model that is an integral part of the SEMM. The resulting mismatch model influences the design of the SU-MIMO precoder that aims to maximize certain transmission criterion. Even though SU-MIMO precoding is considered, a new channel correlation definition, which acts as a metric for the OSEMM, is given that allows for user selection in a multiuser scenario such that optimal performance can be attained for the targeted user. Analytical and simulation results are given that highlight the difference in performance between the two variants of the OSEMM.     

Mechanistic study on DNA mutation of the cytosine methylation reaction at C5 position

DNA methylation is a crucial epigenetic mark connected to conventionally changing the DNA bases, typically by adding methyl groups into DNA bases. Methylation of cytosine at the C5 position (5-methylcytosine) occurs mostly in the context of cytosine-phosphate-guanine dinucleotides, the methylation of which has important impacts on gene regulation and expression. However, the mechanistic details of this reaction are still debatable concerning the concertedness of the key reaction steps and the roles played by the base that abstracts the proton in the β-elimination and water molecules at the active site. To gain a deeper insight into the formation of 5-mehtylcytosine, an extensive density functional theory (DFT) study was performed with the B3LYP functional in conjunction with different basis sets. Our study has clearly established the mechanistic details of this methylation approach, based on which the roles of conserved active site residues, such as glutamic acid and waters, are well understood. Our results show that the reaction of 5-methylcytosine follows a concerted mechanism in which water molecules are critically involved. Moreover, arginine and alanine give more significant catalytic effects than glutamic acid on the 5-methylcytosine process. Considering the effect of Alanine, Arginine, and one water bridging molecule, the activation energy is 31 kJ mol^?1 calculated at B3LYP/6-31G(d) level of theory.     

Sample conditions to avoid pH distortion in RP‐LC

Band deformations might take place for acids and bases in preparative applications and adsorption studies where it is necessary to use overloaded injections. In this study, we focus on how deformations can be prevented without using highly concentrated buffers that may precipitate in the eluent. We have systematically investigated how the elution zones depend on which protolytic form the analyte has when it is dissolved. Basic and acidic model compounds are investigated using eluents with different pH values and the resulting elution profiles are compared when the analytes are dissolved in their protonated and deprotonated form, i.e., in uncharged form or as different kinds of salts. Depending on the analyte's protolytic form, a sample zone is created at the column inlet whose pH deviates, more or less, from the bulk eluent's. If the local adsorption strength in this sample zone is greater than the bulk eluent's, the elution profiles are compressed. Under opposite conditions, the eluted bands are more or less deformed and may even be split; completely different deformations can even take place for different kinds of salt combinations. Explanations of these, and other, effects, together with detailed guidelines for proper sample preparation to avoid peak deformations, are given.