冬青树叶表面的红外光谱特征

用红外衰减全反射技术(ATR)研究了各生长期和不同环境中冬青树叶表面的红外光谱特征.当用黑色塑料袋套在冬青枝条上48 h后,树叶表面的水分有所增加,其它成分变化甚微.当用透明塑料袋套在枝条上48 h后,树叶表面酯类物质的特征峰1 730、1 682 cm-1增加,且峰强度相当.当冬青叶片与甲苯气体接触48 h后,叶片反面酯类物质的特征峰(1 730、1 168、1 039 cm-1)有所减少.同样,叶片正面的酯类物质(1 730、1 168、1 039 cm-1)也有所减少.扫描电镜能谱也证实了叶片反面酯类物质确有减少.     

Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence

Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [Nd^III (phen)₃ (NCX)₃] 0.3EtOH (X = S, 1-S; Se, 1-Se) were designed and prepared. Both compounds show several THz-TDS and LF-Raman peaks in the sub-THz range, with the lowest frequencies of 0.65 and 0.59 THz for 1-S and 1-Se, and 0.75 and 0.61 THz for 1-S and 1-Se, respectively. The peak redshift was observed due to the substitution of SCN⁻ by SeCN⁻. Additionally, temperature-dependent TDS-THz studies showed a thermal blueshift phenomenon, as the peak position shifted to 0.68 THz for 1-S and 0.62 THz for 1-Se at 10 K. Based on ab initio calculations, sub-THz vibrations were ascribed to the swaying of the three thiocyanate/selenocyanate. Moreover, both samples exhibited near-infrared (NIR) emission from Nd (III), and very good thermometric properties in the 300–150 K range, comparable to neodymium (III) oxide-based thermometers and higher than previously reported complexes. Moreover, the temperature dependence of fluorescence and THz spectroscopy analysis showed that the reduction in anharmonic thermal vibrations leads to a significant increase in the intensity and a reduction in the width of the emission and LF absorption peaks. These studies provide the basis for developing new routes to adjust the LF vibrational absorption.     

Strong Hydrogen Bonds in Acetylenedicarboxylic Acid Dihydrate

Acetylenedicarboxylic acid dihydrate (ADAD) represents a complex with strong hydrogen bonding between the carboxylic OH and the water molecule. An X-ray re-examination of the ADAD crystal structure confirms the O^…O distance of the short hydrogen bonds, and clearly shows different bond lengths between the two oxygen atoms with respect to the carbon atom in the carboxyl group, indicating a neutral structure for the complex. The neutral structure was also confirmed by vibrational spectroscopy, as no proton transfer was observed. The diffraction studies also revealed two polymorph modifications: room temperature (α) and low temperature (β), with a phase transition at approximately 4.9 °C. The calculated vibrational spectra are in satisfactory agreement with the experimental spectra. A comparison of the structure and the vibrational spectra between the ADAD and the oxalic acid dihydrate reveals some interesting details. The crystal structures of both crystal hydrates are almost identical; only the O^…O distances of the strongest hydrogen bonds differ by 0.08 Å. Although it was expected that a larger O^…O spacing in the ADAD crystal may significantly change the infrared and Raman spectra, especially for the frequency and the shape of the acidic OH stretching vibration, both the shape and frequency are almost identical, with all subpeaks topped on the broad OH stretching vibration. The O^…O distance dependent are only in- and out-of-plane OH deformations modes. The presence of polarons due to the ionized defects was not observed in the vibrational spectra of ADAD. Therefore, the origin of the broad OH band shape was explained in a similar way to the acid dimers. The anharmonicity of a potential enhances the coupling of the OH stretching with the low-frequency hydrogen bond stretching, which, in addition to the Fermi resonance, structures the band shape of the OH stretching. The fine structure found as a superposition of a broad OH stretching is attributed to Davydov coupling.     

Design and Development of a Bimodal Optical Instrument for Simultaneous Vibrational Spectroscopy Measurements

Vibrational spectroscopy techniques are widely used in analytical chemistry, physics and biology. The most prominent techniques are Raman and Fourier-transform infrared spectroscopy (FTIR). Combining both techniques delivers complementary information of the test sample. We present the design, construction, and calibration of a novel bimodal spectroscopy system featuring both Raman and infrared measurements simultaneously on the same sample without mutual interference. The optomechanical design provides a modular flexible system for solid and liquid samples and different configurations for Raman. As a novel feature, the Raman module can be operated off-axis for optical sectioning. The calibrated system demonstrates high sensitivity, precision, and resolution for simultaneous operation of both techniques and shows excellent calibration curves with coefficients of determination greater than 0.96. We demonstrate the ability to simultaneously measure Raman and infrared spectra of complex biological material using bovine serum albumin. The performance competes with commercial systems; moreover, it presents the additional advantage of simultaneously operating Raman and infrared techniques. To the best of our knowledge, it is the first demonstration of a combined Raman-infrared system that can analyze the same sample volume and obtain optically sectioned Raman signals. Additionally, quantitative comparison of confocality of backscattering micro-Raman and off-axis Raman was performed for the first time.     

叶绿素荧光量子产量的MODIS遥感算法

从荧光量子产量的原理出发,利用 MODIS 卫星数据建立了一种估算量子产量的算法--φ算法.通过 2006 年 3 月 23 日渤海和北黄海的 MODIS 数据计算了荧光量子产量,并与叶绿素荧光效率(cFE)产品进行了比较.结果表明,φ算法是一种更精确的荧光量子产量的估算算法,它有效地避免了 CFE 存在的几个误差来源:包括未考虑浮游植物的"包裹效应"、使用 412nm 的离水辐亮度反演的浮游植物吸收系数以及积分深度过浅.CFE在大部分海域出现负值,还出现了某些高估点;在有效数据范围内,两者存在明显的线性相关关系.φ算法估算的量子产量最高值在0.05左右,这与其它海区测量的值域范围基本一致.除辽东湾东北部和部分近岸水域外,大部分离岸水域在0.001～0.02的范围内.通过对φ算法的误差来源分析,认为发展一种新的反演 678nm 比吸收系数和平均吸收系数的波段比值算法是可行的,也是改进φ算法精度的有效方法.     

Cardiac Troponin Biosensor Designs: Current Developments and Remaining Challenges

Acute myocardial infarction (AMI) is considered as one of the main causes of death, threating human lives for decades. Currently, its diagnosis relies on electrocardiography (ECG), which has been proven to be insufficient. In this context, the efficient detection of cardiac biomarkers was proposed to overcome the limitations of ECG. In particular, the measurement of troponins, specifically cardiac troponin I (cTnI) and cardiac troponin T (cTnT), has proven to be superior in terms of sensitivity and specificity in the diagnosis of myocardial damage. As one of the most life-threatening conditions, specific and sensitive investigation methods that are fast, universally available, and cost-efficient to allow for early initiation of evidence-based, living-saving treatment are desired. In this review, we aim to present and discuss the major breakthroughs made in the development of cTnI and cTnT specific biosensor designs and analytical tools, highlighting the achieved progress as well as the remaining challenges to reach the technological goal of simple, specific, cheap, and portable testing chips for the rapid and efficient on-site detection of cardiac cTnI/cTnT biomarkers in order to diagnose and treat cardiovascular diseases at an incipient stage.     

Molecular Weight Measurement of UG8 Asphaltene Using APCI Mass Spectroscopy

Abstract

Asphaltene molecular weight has been a controversial issue in the past several decades and continues on nowadays. From industrial application point of view, asphaltene molecular weight is important for setting up a heavy oil refining strategy so that the process is efficient and economically viable. If the measured average molecular weight of asphaltene is high and is the true molecular weight, then substantial amount of energy will be needed, in order to break the molecule into light products during refining process. This is likely not an economical option. On the other, if the measured high molecular weight is due to self-association and the true molecular weight is low (e.g., less than 1500 Da), it will be energetically attractive to refiners to develop heavy oil cracking technology. Vapor pressure osmometry (VPO) has been routinely used for measuring molecular weight. However, it measures the apparent molecular weight and is likely not the true molecular weight. In order to unambiguously measure the molecular weight, it is necessary to develop a convincing technology and a reliable experimental procedure that allows one to measure the molecular weight accurately and consistently. We chose the Atmospheric Pressure Chemical Ionization (APCI) technique and Atmospheric Pressure Photo Ionization (APPI) to measure UG8 asphaltene. Both APCI and APPI have mild ionization processes and have been applied to many unstable drug compounds such as proteins and peptides with reliable outcomes. In addition, we measured the sample on two APPI instruments to compare the results. We also demonstrated how one can choose wrong set of operating parameters and lead to erroneous results. The relevant parameters for APCI and APPI are temperature, voltage, and sample concentration. We chose 0.01 mg/mL as the concentration, much below any known critical aggregation concentration. As for temperature and ionization voltage, we varied systematically varied (T = 300–600°C; V = 30–150 V) in order to demonstrate the consistency of the methods and how one can easily make mistake. Through these measurements, an average molecular weight of 400 to 900 Da was obtained for UG8 asphaltene.     

飞秒光电子影像技术对氯丙烯分子的光电离/解离机理的研究

飞秒光电子影像技术结合飞行时间质谱对氯丙烯（C3H5Cl）在200 nm、400 nm、800 nm飞秒脉冲下的光电离/解离机理进行了研究。实验结果表明氯丙烯的光电离/解离机理与激光波长存在依赖关系。分析发现,在短波长200 nm时,母体分子C3H5Cl以双光子电离为主要通道,而其他的碎片离子则来源于C3H5Cl+的解离。当波长向长波方向变化时,例如800 nm时,C3H5Cl中间态的解离就开始占主导地位,碎片离子的信号也相应增强。此外,光电子能谱进一步证实了在400 nm和800 nm时存在来源于中性碎片的光电子,而这些中性碎片又是由C3H5Cl的中间态直接解离而产生的。这意味着,在长波400 nm和800 nm时,母体分子可能被激发到寿命较短的中间解离态,从而解离产生中性碎片,导致光解离过程在长波段占有重要角色。     

Recent Advances in Sandwich SERS Immunosensors for Cancer Detection

Cancer has been one of the most prevalent diseases around the world for many years. Its biomarkers are biological molecules found in the blood or other body fluids of people with cancer diseases. These biomarkers play a crucial role not only in the diagnosis of cancer diseases, but also in risk assessment, selection of treatment methods, and tracking its progress. Therefore, highly sensitive and selective detection and determination of cancer biomarkers are essential from the perspective of oncological diagnostics and planning the treatment process. Immunosensors are special types of biosensors that are based on the recognition of an analyte (antigen) by an antibody. Sandwich immunosensors apply two antibodies: a capture antibody and a detection antibody, with the antigen ‘sandwiched’ between them. Immunosensors’ advantages include not only high sensitivity and selectivity, but also flexible application and reusability. Surface-enhanced Raman spectroscopy, known also as the sensitive and selective method, uses the enhancement of light scattering by analyte molecules adsorbed on a nanostructured surface. The combination of immunosensors with the SERS technique further improves their analytical parameters. In this article, we followed the recent achievements in the field of sandwich SERS immunosensors for cancer biomarker detection and/or determination.     

Electron Transfer in a Bio-Photoelectrode Based on Photosystem I Multilayer Immobilized on the Conducting Glass

A film of ~40 layers of partially oriented photosystem I (PSI) complexes isolated from the red alga Cyanidioschyzon merolae formed on the conducting glass through electrodeposition was investigated by time-resolved absorption spectroscopy and chronoamperometry. The experiments were performed at a range of electric potentials applied to the film and at different compositions of electrolyte solution being in contact with the film. The amount of immobilized proteins supporting light-induced charge separation (active PSI) ranged from ~10%, in the absence of any reducing agents (redox compounds or low potential), to ~20% when ascorbate and 2,6-dichlorophenolindophenol were added, and to ~35% when the high negative potential was additionally applied. The origin of the large fraction of permanently inactive PSI (65–90%) was unclear. Both reducing agents increased the subpopulation of active PSI complexes, with the neutral P700 primary electron donor, by reducing significant fractions of the photo-oxidized P700 species. The efficiencies of light-induced charge separation in the PSI film (10–35%) did not translate into an equally effective generation of photocurrent, whose internal quantum efficiency reached the maximal value of 0.47% at the lowest potentials. This mismatch indicates that the vast majority of the charge-separated states in multilayered PSI complexes underwent charge recombination.