Excited-State Dynamics of Thienoguanosine,an Isomorphic Highly Fluorescent Analogue of Guanosine

Thienoguanosine (^thG) is an isomorphic analogue of guanosine with promising potentialities as fluorescent DNA label. As a free probe in protic solvents, ^thG exists in two tautomeric forms, identified as the H1, being the only one observed in nonprotic solvents, and H3 keto–amino tautomers. We herein investigate the photophysics of ^thG in solvents of different polarity, from water to dioxane, by combining time-resolved fluorescence with PCM/TD-DFT and CASSCF calculations. Fluorescence lifetimes of 14.5–20.5 and 7–13 ns were observed for the H1 and H3 tautomers, respectively, in the tested solvents. In methanol and ethanol, an additional fluorescent decay lifetime (≈3 ns) at the blue emission side (λ≈430 nm) as well as a 0.5 ns component with negative amplitude at the red edge of the spectrum, typical of an excited-state reaction, were observed. Our computational analysis explains the solvent effects observed on the tautomeric equilibrium. The main radiative and nonradiative deactivation routes have been mapped by PCM/TD-DFT calculations in solution and CASSCF in the gas phase. The most easily accessible conical intersection, involving an out-of plane motion of the sulfur atom in the five-membered ring of ^thG, is separated by a sizeable energy barrier (≥0.4 eV) from the minimum of the spectroscopic state, which explains the large experimental fluorescence quantum yield.     

The Plasticity of the Carbohydrate Recognition Domain Dictates the Exquisite Mechanism of Binding of Human Macrophage Galactose-Type Lectin

The human macrophage galactose-type lectin (MGL), expressed on macrophages and dendritic cells (DCs), modulates distinct immune cell responses by recognizing N-acetylgalactosamine (GalNAc) containing structures present on pathogens, self-glycoproteins, and tumor cells. Herein, NMR spectroscopy and molecular dynamics (MD) simulations were used to investigate the structural preferences of MGL against different GalNAc-containing structures derived from the blood group A antigen, the Forssman antigen, and the GM2 glycolipid. NMR spectroscopic analysis of the MGL carbohydrate recognition domain (MGL-CRD, C181-H316) in the absence and presence of methyl α-GalNAc (α-MeGalNAc), a simple monosaccharide, shows that the MGL-CRD is highly dynamic and its structure is strongly altered upon ligand binding. This plasticity of the MGL-CRD structure explains the ability of MGL to accommodate different GalNAc-containing molecules. However, key differences are observed in the recognition process depending on whether the GalNAc is part of the blood group A antigen, the Forssman antigen, or GM2-derived structures. These results are in accordance with molecular dynamics simulations that suggest the existence of a distinct MGL binding mechanism depending on the context of GalNAc moiety presentation. These results afford new perspectives for the rational design of GalNAc modifications that fine tune MGL immune responses in distinct biological contexts, especially in malignancy.     

Kinetics of carbon steel dissolution in ammonium chloride solution containing sodium thiosulfate

The dissolution behavior of carbon steel in ammonium chloride (NH₄Cl) solution containing sodium thiosulfate (Na₂S₂O₃) of various concentrations (0.01 and 0.1 M) was investigated using electrochemical impedance spectroscopy (EIS) and other nonelectrochemical techniques. The weight loss and polarization measurements indicate a significant increase in the NH₄Cl corrosion rate of carbon steel on addition of Na₂S₂O_3. The EIS measurements exhibited two capacitive loops at multiple direct current (dc) potentials for both the concentrations. Electrical equivalent circuit (EEC) and reaction mechanism analysis (RMA) were employed to analyze the impedance data. A four-step mechanism with two intermediate adsorbate species of same charge was proposed to explain the dissolution behavior of carbon steel in the given system. The surface coverage values enumerated that the surface was entirely covered with adsorbed species unlike in the pure NH₄Cl system. Charge transfer resistance and polarization resistance values estimated from RMA parameters indicate the increase in a dissolution rate with dc potential. The surface morphology was inspected via field emission scanning electron microscopy, and the corrosion products including surface state of carbon steel electrode were analyzed using energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy.     

Enhancing the Viscosity-Sensitive Range of a BODIPY Molecular Rotor by Two Orders of Magnitude

Molecular rotors are a class of fluorophores that enable convenient imaging of viscosity inside microscopic samples such as lipid vesicles or live cells. Currently, rotor compounds containing a boron-dipyrromethene (BODIPY) group are among the most promising viscosity probes. In this work, it is reported that by adding heavy-electron-withdrawing −NO₂ groups, the viscosity-sensitive range of a BODIPY probe is drastically expanded from 5–1500 cP to 0.5–50 000 cP. The improved range makes it, to our knowledge, the first hydrophobic molecular rotor applicable not only at moderate viscosities but also for viscosity measurements in highly viscous samples. Furthermore, the photophysical mechanism of the BODIPY molecular rotors under study has been determined by performing quantum chemical calculations and transient absorption experiments. This mechanism demonstrates how BODIPY molecular rotors work in general, why the −NO₂ group causes such an improvement, and why BODIPY molecular rotors suffer from undesirable sensitivity to temperature. Overall, besides reporting a viscosity probe with remarkable properties, the results obtained expand the general understanding of molecular rotors and show a way to use the knowledge of their molecular action mechanism for augmenting their viscosity-sensing properties.     

Chiral one‐dimensional hydrogen‐bonded architectures constructed from single‐enantiomer phosphoric triamides

The two single‐enantiomer phosphoric triamides N‐(2,6‐difluorobenzoyl)‐N′,N′′‐bis[(S)‐(−)‐α‐methylbenzyl]phosphoric triamide, [2,6‐F₂‐C₆H₃C(O)NH][(S)‐(−)‐(C₆H₅)CH(CH₃)NH]₂P(O), denoted L‐1 , and N‐(2,6‐difluorobenzoyl)‐N′,N′′‐bis[(R)‐(+)‐α‐methylbenzyl]phosphoric triamide, [2,6‐F₂‐C₆H₃C(O)NH][(R)‐(+)‐(C₆H₅)CH(CH₃)NH]₂P(O), denoted D‐1 , both C₂₃H₂₄F₂N₃O₂P, have been investigated. In their structures, chiral one‐dimensional hydrogen‐bonded architectures are formed along [100], mediated by relatively strong N—H…O(P) and N—H…O(C) hydrogen bonds. Both assemblies include the noncentrosymmetric graph‐set motifs R₂²(10), R₂¹(6) and C₂²(8), and the compounds crystallize in the chiral space group P1. Due to the data collection of L‐1 at 120 K and of D‐1 at 95 K, the unit‐cell dimensions and volume show a slight difference; the contraction in the volume of D‐1 with respect to that in L‐1 is about 0.3%. The asymmetric units of both structures consist of two independent phosphoric triamide molecules, with the main difference being seen in one of the torsion angles in the OPNHCH(CH₃)(C₆H₅) part. The Hirshfeld surface maps of these levo and dextro isomers are very similar; however, they are near mirror images of each other. For both structures, the full fingerprint plot of each symmetry‐independent molecule shows an almost asymmetric shape as a result of its different environment in the crystal packing. It is notable that NMR spectroscopy could distinguish between compounds L‐1 and D‐1 that have different relative stereocentres; however, the differences in chemical shifts between them were found to be about 0.02 to 0.001 ppm under calibrated temperature conditions. In each molecule, the two chiral parts are also different in NMR media, in which chemical shifts and P–H and P–C couplings have been studied.     

近红外光谱结合共识模型快速检测果酒的总酚含量

果酒发酵中的多酚是引起果酒口感、颜色变化的重要因素。为保证果酒品质,有必要开发一种快速监测发酵过程中多酚含量变化的技术。收集不同批次成熟期的蓝莓、桑葚为原料,分别碾压成汁,同时按比例混合二者,于小型发酵罐进行发酵。通过离线收集不同发酵时段的发酵液于离心管,高速离心后取上清液置于棕色瓶保存,共计得到48个果酒发酵样本。将上清液置于三个平行样比色皿,以傅里叶快速变换近红外光谱仪(FT-NIR)采集其透射光谱,取平均值作为该样本的光谱信号。然后将棕色瓶内的发酵液以国标法(即以标准液的吸光度值制定标准曲线)测定各样品的总酚含量,以duplex法计算样本光谱之间的距离且按2∶1的比例划分为训练集和预测集。采用间隔偏最小二乘法(iPLS)将训练集样本的透射光谱与总酚含量之间构建定量模型,间隔数从2依次变化到60个。该研究创新之处是使用共识方法融合多个已构建好的iPLS成员模型,按一定的共识规则分配权系数。通过各成员模型交互验证的残差及其残差之间的相关性来优化各成员模型的线性组合,以拉格朗日乘数法求解各成员模型的权系数,使间隔偏最小二乘-共识模型(consensual iPLS,CiPLS)的交互验证均方根误差最小。相比于全局PLS模型、划分不同间隔数量时的iPLS模型,CiPLS均具有较小的预测误差。当划分39个间隔时由三个iPLS成员模型(即14th,16th,18th)组成的共识模型误差最小为124.2,交互验证相关系数为0.944,对预测集样本的预测均方根误差为163.4,预测相关系数为0.931,预测性能均优于PLS和iPLS模型。另外,作为对比选用连续投影算法与无信息变量剔除法来优化光谱模型,其预测性能均不及本文提出的共识模型。分析各iPLS模型预测残差之间的相关性,发现共识模型主要是融合那些具有较高预测性能且模型间较低相关性的成员模型。结果表明,光谱分析结合共识方法可提高回归模型的预测精度、减少建模所需变量数,能够用于果酒总酚含量的离线快速检测。     

Dielectrophoretically Modulated Optical Spectroscopy of Colloidal Nanoparticle Solutions in Microfluidic Channels

Optical spectroscopic techniques (e.g., extinction, scattering, and fluorescence spectroscopies) are important for the analysis of colloidal solutions of nanoparticles (NPs). They are routinely applied to plasmonic and quantum-dot NP samples assuming that these contain a single population of particles with modest size and shape dispersity. However, these spectroscopic techniques become less effective when the sample is a mixture of particles with different sizes, shapes, or composition. Here, an original microfluidic method is proposed for the optical spectroscopic analysis of colloidal NP solutions that combines periodic trapping of NPs by dielectrophoresis (DEP) with in situ optical extinction spectroscopy. The periodic trapping leads to modulation of the continuously monitored optical spectrum depending on the DEP properties of the NPs. DEP-modulated spectroscopy is demonstrated using colloidal gold NPs as small as 40 nm diameter. It is found that the DEP modulation is significantly enhanced when employing suitable microfluidic flow over a multielectrode array. Finally, it is shown that the method can identify and characterize the NP species simultaneously present in a mixture of 40 and 80 nm gold NPs, opening the way toward optical spectroscopic analysis of higher complexity NP mixtures through the combination of the DEP-modulated spectroscopy with chemometric methods.     

湿度对水泥生料近红外光谱检测的影响及补偿方法

近红外光谱检测已被应用于水泥生料成分的快速检测,但现场环境中的湿度等因素会对光谱产生干扰,从而降低检测精度。为了提高检测精度,在实验分析湿度对水泥生料近红外光谱检测影响的基础上研究了补偿方法。在水泥厂选取了24份水泥生料样本,其中18份作为校正集,6份作为验证集;水泥生料中的有效成分为SiO2,Al2O3,Fe2O3和CaCO3,各成分含量的标准值由X射线荧光光谱分析测出。首先,将校正集的18份样本每份重复装样测5次光谱,用得到的90个光谱建立模型Ⅰ;再每份样品制作5个湿度梯度样本,其获得过程为,先将样本放置在电加热平台上,用玻璃棒将样本摊平,180℃下加热30 min,再将样本放置在散热片上进行降温,待样品恢复室温后取出进行第一次光谱扫描,得到1个光谱,将测量后的样本放入搅拌器,使用装有去离子水的喷雾器对其喷雾两次,然后搅拌30 s混合均匀,测量混合后的样本得到下一个光谱,重复该过程,得到具有湿度梯度的5个光谱。所有样本均采用烘干法进行湿度测量,样本湿度变化区间在0.6%~2%以内。对每个湿度梯度的样本测量1次,用得到的这90个光谱建立模型Ⅱ。然后,将验证集的6份样本每份制作5个湿度梯度,获取方式与校正集相同,对每个湿度梯度的样本测量1次,得到30个光谱。所有光谱均采用多元散射校正预处理,拟合波段选择4000~5000 cm^-1,建模方法采用偏最小二乘法。比较同一份样本的5个湿度梯度,可以看到在5200 cm^-1处光谱差异最大,在其他位置也有肉眼可见的明显差异,因此,湿度变化对全波段光谱有明显的影响。最后,将这30个光谱输入模型Ⅰ与模型Ⅱ进行验证,并对比模型Ⅰ与模型Ⅱ的预测均方根误差RMSEP。模型Ⅱ中SiO2,Al2O3,Fe2O3和CaCO3的预测均方根误差RMSEP比模型Ⅰ分别减小了25%,31.3%,33.3%和25%。实验结果表明,水泥生料样本湿度对近红外光谱模型的预测结果具有一定的影响,采用具有湿度梯度的样本进行建模可有效降低湿度对预测结果的影响。     

基于科赫曲线分形结构太赫兹带通滤波器

太赫兹滤波器是太赫兹通信、太赫兹成像和太赫兹检测等太赫兹应用系统中不可或缺的功能器件。按照不同的分类方式,滤波器有不同的种类,常见的按照选频功能可分为高通滤波器、低通滤波器、带阻滤波器和带通滤波器。为了实现在太赫兹波段的滤波效果,世界各地的研究人员利用不同的结构、材料和控制方式实现了功能各异的太赫兹滤波器,但是考虑到设计的器件要应用到太赫兹系统中,成本低廉、结构简单、性能优越的太赫兹滤波器一直是研究人员的追求。分形概念自提出以来在很多研究领域都有了快速发展,但是在太赫兹波段的应用还不是很常见,特别是应用于太赫兹功能器件的设计。引入分形中科赫曲线的概念设计并制备了一种新型的太赫兹带通滤波器,该滤波器是在金属薄膜上刻蚀出科赫曲线分形结构,当太赫兹波垂直入射到该滤波器时候实现了在太赫兹波段的窄带滤波。在滤波器的设计过程中,追求理论与实验相结合,首先在电磁仿真软件中建立科赫曲线分形结构滤波器模型进行计算,探究分形结构应用于太赫兹波段进行滤波的可行性,在进行多次计算之后得到优化后的尺寸和结构,然后根据优化后的尺寸加工出科赫曲线分形结构太赫兹滤波器样品,并且将样品放在太赫兹时域光谱系统中进行实验测量,得到实验数据后与仿真结果进行比较。在仿真中利用了时域有限差分法模拟科赫曲线分形结构太赫兹带通滤波器的传输特性,优化后的仿真结果表明:滤波器的谐振频率为0.715 THz,透射系数能够达到0.92,-3 dB带宽为21.9 GHz,将仿真得到的散射参数进行S参数反演得到了太赫兹滤波器样品的电磁参数,这在理论上分析了太赫兹波在谐振点处产生透射增强的原因。利用飞秒激光微加工系统制备了尺寸优化后的科赫曲线分形结构太赫兹带通滤波器样品,然后使用太赫兹时域光谱系统对样品的传输特性进行测试,对实验得到的时域数据进行快速傅里叶变换之后得到频域数据,再把频域数据进行归一化处理后与之前的电磁仿真结果进行对比,发现实验测得的结果与电磁软件仿真得到的结果较为吻合。