Tip-Enhanced Raman Spectroscopy and Mapping of Graphene Sheets

Abstract: Single graphene sheets, a few graphene layers, and bulk graphite, obtained via both micromechanical cleavage of highly oriented pyrolytic graphite and carbon vapor deposition methods, were deposited on a thin glass substrate without the use of any chemical treatment. Micro-Raman spectroscopy, tip-enhanced Raman spectroscopy (TERS), and tip-enhanced Raman spectroscopy mapping (TERM) were used for characterization of the graphene layers. In particular, TERM allows for the investigation of individual graphene sheets with high Raman signal enhancement factors and allows for imaging of local defects with nanometer resolution. Enhancement up to 560% of the graphene Raman band intensity was obtained using TERS. TERM (with resolution better than 100 nm) showed an increase in the number of structural defects (D band) on the edges of both graphene and graphite regions.     

还原态烟酰胺腺嘌呤二核苷酸拉曼光谱研究

还原态烟酰胺腺嘌呤二核苷酸(NADH)在维持细胞生长、分化、能量代谢以及细胞保护方面起着非常重要的作用,NADH的无创在体检测具有非常重要的意义。运用激光拉曼散射实验和密度泛函理论(DFT)计算研究了200～3 300 cm-1光谱范围内NADH分子的振动模式特性。DFT计算采用了B3LYP杂化方法,并选用了极化6-311+G(d,p)基组。为了准确的分析NADH分子的振动模式和频率,首先运用B3LYP/6-311+G(d,p)理论对NADH分子的基态结构进行了几何优化,并计算了基态结构NADH分子的各个键长和键角。同时考虑到DFT计算中的非谐性,运用波数线性标度方法对所有计算所得振动模式波数重新进行了标度。重新标度后,DFT计算所得的振动模式波数与激光拉曼散射实验观测到的拉曼峰波数吻合的很好：在200～3 300 cm-1整个光谱范围内,计算与实验结果具有非常好的线性相关性,而且大部分振动模式的计算与实验之间的偏差都小于5 cm-1。此外,讨论了实验观察所得拉曼光谱的分子振动模式归属,分析了NADH分子中腺嘌呤、烟酰胺、及二核苷酸的特征振动模式,并初步提出了运用拉曼光谱实现NADH快速准确无创在体检测的方法。位于732 cm-1处的拉曼峰是腺嘌呤的特征振动模式,而且可以选为检测NADH分子的最特征拉曼峰。位于1 690 cm-1处的拉曼峰是烟酰胺的特征振动模式,可以选为进一步准确检测NADH分子的另一个特征拉曼峰。位于1 086和1 339 cm-1两处拉曼峰的组合可以作为二核苷酸的特征振动模式,用于进一步更准确的检测NADH分子。所以在运用拉曼光谱法实现NADH快速准确无创在体检测时,可以首先运用位于732 cm-1处NADH分子的最特征振动模式进行快速检测,然后再运用位于1 690 cm-1及1 086和1 339 cm-1组合等特征振动模式进行准确分析。     

高温还原氧化石墨烯膜及其导热性能

采用氧化还原法制备了结构致密且具有较高柔韧性的石墨烯薄膜,探究了薄膜经过较高退火温度还原后结构变化,并通过T型稳态法测量了其热导率,研究了还原温度对薄膜热导率和力学性能的影响。结果表明,高温还原有助于氧化石墨烯中含氧官能团的去除和sp2杂化碳晶格的恢复,并且温度越高还原效果越好。当还原温度高达2800℃时,在200~350 K温度范围内石墨烯膜的热导率在336.9~436 W·m^-1·K^-1之间,伴随着温度的升高,热导率有先增大后减小的趋势。     

Using Reduced Graphene Oxide to Generate Q-Switched Pulses in Er-Doped Fiber Laser

Using the reduced graphene oxide(rGO) as a saturable absorber(SA) in an Er-doped fiber(EDF) laser cavity,we obtain the Q-switching operation. The rGO SA is prepared by depositing the GO on fluorine mica(FM) using the thermal reduction method. The modulation depth of rGO/FM is measured to be 3.2%. By incorporating the rGO/FM film into the EDF laser cavity, we obtain stable Q-switched pulses. The shortest pulse duration is3.53 μs, and the maximum single pulse energy is 48.19 nJ. The long-term stability of working is well exhibited.The experimental results show that the rGO possesses potential photonics applications.     

Infrared Difference Spectroscopy as a Physical Tool to Study Biomolecules

Abstract

This brief review focuses on the information that can be obtained for biomolecules, especially proteins, by using the technique infrared-induced difference spectroscopy.     

石墨烯包裹的爆米花中空结构的FeS纳米颗粒作为钠离子电池阳极的性能研究

用一步水热法合成多孔的爆米花形状的由还原石墨烯包裹的FeS纳米颗粒,该复合颗粒作为钠离子电池阳极使用。多孔结构有助于该复合物展现出优越的循环稳定性和速率性能。在电流密度为100 mA g-1时,100次循环之后该复合物依然保持可逆比容量552 mA h g-1;在电流密度为5000 mA g-1时,表现出比容量为307 mA h g-1。此外,Na, S 和 Fe的相图分析揭露了Na 和 FeS 在充放电过程中的氧化还原机制。     

Graphene oxide as a substrate for Raman enhancement

We report the properties of graphene oxide, a two-dimensional carbon nanomaterial, as a substrate for surface-enhanced Raman scattering. The graphene oxide substrate produced Raman enhancement for rhodamine 6G, melamine, and cephalexin. Intense characteristic D and G peaks of graphene oxide were observed when positively charged rhodamine 6G and melamine were used as the Raman probe. We attribute the appearance of D and G peaks to the aggregation of negatively charged graphene oxide.     

拉曼光谱技术的汽油组分含量测定

为实现汽油中所含组分含量的快速测定,对93号、97号汽油,芳烃、烯烃、苯、甲醇、乙醇等几类物质,以及往汽油中添加几类物质后的410个汽油混合物进行拉曼光谱检测。将获取的原始拉曼光谱经过有效波段提取、平滑去噪、基线扣除、数据归一化等一系列预处理过程,最终提取出每个汽油混合样品光谱中所含的33个特征峰信息,依据现行的国标检测方法,以气相色谱法测定的汽油中各组分含量值为基础,结合化学计量学多重回归分析方法,建立了汽油组分含量测定模型。经过比较,使用多输出最小二乘支持向量回归机(MLS-SVR)建立的模型优于偏最小二乘(PLS)模型。MLS-SVR模型对汽油中芳烃、烯烃、苯、甲醇、乙醇测定精度均较好,预测均方根误差(RMSEP)分别为0.27%,0.30%,0.16%, 0.17%, 0.12%;相应的相关系数(r)为0.999 2,0.998 4,0.998 5,0.992 6,0.996 8。通过对未知混合汽油样品的测定,证明了该方法具有较好的推广预测精度,预测均方根误差不超过0.5%,能够满足工业中的测量需求。拉曼光谱结合多输出最小二乘支持向量机为汽油组分测定提供了一种高精确、快捷、方便的测定方法。     

人肝癌组织细胞的激光光镊拉曼光谱研究

激光光镊与拉曼光谱相结合形成的激光光镊拉曼光谱系统(LTRS)已用于分析生物组织标本,可对单个活细胞进行操控和光谱收集。从拉曼光谱特征峰位置、强度和线宽可得到有关细胞的组成、结构及细胞内物质相互作用的信息。文章应用LTRS系统,分析了来自人的恶性肝癌组织的不同病变部位标本,包括肝癌组织细胞、肝癌癌旁细胞和远离肝癌组织的肝脏正常的组织细胞,观察到了随肝癌的病变部位变化所出现的一些有趣的拉曼光谱峰的变化。正常的肝组织细胞在1 070和1 266 cm-1处的峰很明显,而肝癌和肝癌癌旁组织细胞的这两个峰则不明显,肝正常组织细胞的1 445 cm-1峰明显高于肝癌和肝癌癌旁组织细胞。已知1 070 cm-1峰代表脂类和核酸,1 266和1 445 cm-1峰代表脂类和蛋白。引起这些峰变化的物质很可能参与了肝癌的发生。上述初步研究结果表明：单细胞激光光镊拉曼光谱可以区分肝癌的不同病变部位,将是检测和分析肝癌组织标本的一种很好的方法。     

乳腺肿瘤周边组织的拉曼光谱研究

使用REMSHAW显微共焦拉曼光谱仪测量了40例手术切除乳腺肿瘤周边(肿块边约5 mm)组织的拉曼光谱.通过对浸润性导管癌、乳腺增生、纤维腺瘤等乳腺肿瘤周边组织的拉曼光谱分析,发现不同乳腺肿瘤周边组织的拉曼光谱有显著差异.这些差异在肿瘤诊断中,可作为乳腺癌和其他乳腺肿瘤拉曼光谱的特征,为乳腺疾病诊断提供依据.乳腺肿瘤周边组织的拉曼光谱对乳腺肿瘤诊断具有重要的价值.     

鼻咽癌离体组织拉曼光谱的测量

拉曼光谱分析技术在探测与组织病理学相关的分子变化方面具有特别的潜力和优势,并且使无损、实时、快速的光学诊断成为可能.采用785 nm半导体激光器,透射式的全息光栅,背向感光、深度耗尽的CCD探测器及特殊设计的光纤拉曼探头构建了一台快速拉曼光谱测试装置.所设计的光纤拉曼探头可在减少荧光信号和瑞利散射影响的同时,最大限度地收集生物组织的拉曼信号,同时解决了平面光栅衍射光束的谱线弯曲问题,提高了仪器的信噪比,使装置具有较高的灵敏度并可快速测量获得人体组织的近红外拉曼信号.通过新鲜猪肉的脂肪和肌肉组织的拉曼光谱信号的检测,验证了测试装置的良好性能; 在此基础上,研究了鼻咽癌组织样品存放时间对拉曼光谱的影响,并在1～5 s时间内快速测量获得了人离体鼻咽癌组织的近红外拉曼光谱.     

Reduced Graphene Oxide decorated with Manganese Cobalt Oxide as Multifunctional Material for Mechanically Rechargeable and Hybrid Zinc–Air Batteries

Spinel MnCo₂O₄ nanoparticles on nitrogen‐doped reduced graphene oxide (MnCo₂O₄/NGr) are synthesized for advanced zinc–air batteries with remarkable cyclic efficiency and stability. The synthesized MnCo₂O₄/NGr exhibits good oxygen‐reduction reaction (ORR) activity with half‐wave potential E _1/2 of 0.85 V (vs reversible hydrogen electrode (RHE)), comparable to commercial Pt/C with E _1/2 of 0.88 V (vs RHE) along with superior oxygen electrode activity ΔE = 0.91 V for the ORR/OER (oxygen‐evolution reaction) in alkaline media. Durability tests confirm that MnCo₂O₄/NGr is more stable than Pt/C in alkaline environment. MnCo₂O₄/NGr functions with stable discharge profile of 1.2 V at 20 mA cm^?2, large discharge capacity of 707 mAh g^?1_Zn at 40 mA cm^?2 and a high energy density of 813 Wh kg^?1_Zn in a mechanically rechargeable zinc–air battery. The electrically rechargeable MnCo₂O₄/NGr zinc–air battery displays hybrid behavior with both Faradaic and oxygen redox charge–discharge characteristics, operating at higher voltage and providing higher power density and excellent cyclic efficiency of 86% for over 100 cycles compared to Pt/C with efficiency of around 60%. Moreover, hybrid zinc–air battery operates with a stable and energy efficient profile at different current densities.     

Vibrational Spectroscopy as a Promising Tool to Study Enzyme-Carrier Interactions: A Review

Abstract

The high selectivity and specificity together with the catalytic activity of enzymes lead them to be a key tool in biotechnology industries. The enzyme immobilization on a carrier material facilitates the reuse of the enzyme and improves its stability. This article is a comprehensive review that reports papers in which different enzymes have been immobilized on distinct carrier materials and enzyme-carrier interactions were evaluated by infrared and/or Raman spectroscopy. Vibrational spectroscopy was used to inspect the spectral bands of different classes of enzymes before and after their immobilization on carriers. In fact, the characteristic spectral bands that prove the interaction enzyme-carrier are related with the amide functional groups of enzymes. In addition, those interactions are characterized by the shift, broadening, or increment on intensity of specific bands in reference to the spectrum of their carrier material. In this review, 20 of these studies used infrared spectroscopy and only three used Raman spectroscopy. The use of both vibrational spectroscopy techniques is increasingly due to their proved capacity to characterize the enzyme-carrier interactions without damaging them.     

氧化钨纳米线结构相变的拉曼光谱研究

本文利用拉曼光谱技术对氧化钨纳米线结构随激光功率改变而变化的情况进行了研究。研究结果表明氧化钨纳米线在一定功率的激光照射下被氧化成了三氧化钨纳米线;随着激光功率的进一步增大,纳米线温度进一步升高,三氧化钨纳米线由开始的单斜相向正交相结构过渡。实验证实三氧化钨纳米线的相变过程是可逆的,而之前的氧化过程是不可逆的。     

Synthesis and Characterization of Poly(vinyl pyrrolidone)/Reduced Graphene Oxide Nanocomposite

Poly(vinyl pyrrolidone) (PVP)/reduced graphene oxide (RGO) nanocomposites were synthesized by reducing graphene oxide in the polymer matrix at different temperatures. The effects of the GO content on the properties of the nanocomposites were investigated by Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The degree of dispersion of GO in the PVP matrix was examined by field-emission scanning electron microscopy. The results showed that both GO and RGO were well dispersed in the PVP matrix. Under low filler content, the improvement of onset decomposition temperatures of PVP nanocomposites was not obviously observed, but the amounts of residual char of the PVP nanocomposites were clearly increased. In addition, the decomposition temperature peak values of the PVP nanocomposites were increased, while the peak was broadened.     

还原石墨烯氧化物-银纳米线柔性复合电极的制备与性能研究

制备了一种具有高导电性、高透过率以及良好的柔性和机械稳定性的还原石墨烯氧化物(RGO)-银纳米线(AgNW)复合电极.将低浓度的AgNW旋涂在制备的RGO薄膜上,使AgNW搭接在RGO的晶界、褶皱处,提高了RGO薄膜的载流子迁移能力.在保证透过率的前提下,提高复合薄膜的导电性能.结合薄膜转写工艺,制备了电阻为420 Ω/口且透过率达62％的RGO-AgNW柔性复合电极.该复合电极具有良好的柔性以及机械稳定性,随着弯折次数的增加,电阻没有明显变化.     

还原石墨烯光学波段复折射率及消光性能研究

在对氧化和还原石墨烯近紫外到近红外波段反射率谱测量的基础上,利用Kramers-Kronig关系计算其复折射率,并反推反射率与光谱分析确定误差水平;运用T矩阵法计算其在该波段的吸收和消光效率因子,分析其消光和吸收性能.结果表明,反推反射率值与实测值误差在10~(-6)量级,且其吸收谱线特征与复折射率虚部吻合;还原石墨烯的可见光-近红外消光和吸收较强,但紫外消光和吸收较弱;氧化石墨烯在紫外-可见光波段的消光和吸收较强,但在近红外波段迅速减弱.因此,该计算方法在两种材料上适用,且氧化和还原石墨烯均可用作宽波段的光吸收或消光材料,但还原石墨烯近紫外波段以及氧化石墨烯近红外波段的性能有待改善.     

拉曼光谱在危地马拉翡翠矿物组成中的应用研究

危地马拉是缅甸之外的另一个翡翠的商业性产地,危地马拉翡翠通常是多种矿物成分的集合体,其矿物组成具有特色,与缅甸翡翠的不同。以危地马拉紫色和灰绿色翡翠为研究对象,通过激光拉曼光谱测试分析,对其结构特征及共生矿物组成特点进行了研究。结果表明,危地马拉翡翠中的主要组成矿物为硬玉,并伴有多种共生矿物。危地马拉翡翠的共生矿物包括五类,其中深色共生矿物为角闪石,白云石,绿辉石和绿泥石,浅色共生矿物为磷灰石。其中角闪石,白云石,绿辉石和绿泥石也是缅甸翡翠中常见的共生矿物,而磷灰石在缅甸翡翠中几乎不可见。     

Ultrafine Mo-Doped Co_2P Nanorods Anchored on Reduced Graphene Oxide as Efficient Electrocatalyst for the Hydrogen Evolution Reaction

One-dimensional(1 D) transition metal phosphides(TMPs) with large specific surface areas,high charge transfer efficiency and excellent electrical conductivity have attracted significant attention in hydrogen evolution reaction(HER) as versatile and active catalysts.Herein,the sub-4 nm Mo-Co₂ P ultrafine nanorods(NRs) anchored on reduced graphene oxide(rGO) were successfully synthesized by a colloidal mesostructured strategy.Electrochemical test results reveal that the Mo-Co₂