作者承认空军研究实验室的下UES分包合同＃S-932-19-MR002的支持。作者进一步确认设备的支持来自纽约州研究生研究和教学计划（GRTI / GR15）。

1.预分析样品制备<ol><li>分离油墨从车辆功能性颗粒:离心<ol><li>基于初始油墨配方，计算需要多少墨水样品需要获得最小2.0克的颗粒沉淀物。例如，如果墨是10体积％的陶瓷和陶瓷的密度是6.67克/厘米3，则最小为3.0毫升墨水的需要，以产生2.0克沉积物。 </li><li>吸管的至少最低要求的墨量到离心管中。离心管的选择应根据所需的油墨量和管材料的惰性至油墨溶剂来制备。 </li><li>将管离心机。离心机和旋转速率的选择将由以沉淀墨粒子所需的重力决定。一个标准的实验室离心机像SORVALL ST16离心机与TX-200水平转头通常是足够的。 </li><li>计划离心机旋转墨在旋转RA德和必要的时间，以产生一清晰的上清液。对于这里使用的离心机，典型的费率和时间是3000 - 4000转分钟的30分钟和90。到达正确的转速和必需的时间以沉淀的墨水可能需要反复试验，因为相同的平均颗粒尺寸的连油墨可具有不同的粒度分布。 </li></ol></li><li>分离后的样品处理:去除上清液，样品洗涤，干燥<ol><li>一旦上层清液已经实现，从离心机取出离心管中。 </li><li>滗析出上清液，并保存以备将来可能分析带盖玻璃样品瓶。功能性微粒是现在残存的离心管中。 </li><li>倾析后，将未加帽的离心管在纸巾上倒置，并允许额外的上清滴出，持续1分钟。 </li><li>从纸巾取出管并通过向冲洗沉淀的颗粒管大约2毫升在油墨制剂中所用的相同组成的新鲜溶剂。请注意，此溶剂将只摸沉淀在离心管中颗粒的最上面的层。滗出溶剂。重复漂洗循环三次。 </li><li>最终漂洗周期之后，将未加帽的离心管在纸巾上倒置，并允许额外的溶剂滴出约5分钟。 </li><li>使用一个薄的金属刮刀从离心管的底部除去沉积物，并蔓延到一个干净的，干燥的表玻璃。使用不起毛的非研磨棉签或干净的铲尖从小勺除去多余的颗粒。 </li><li>将表面皿置于50℃的烘箱，并允许该颗粒干燥24小时。炉子的温度应保持在相对低，以最小化降解吸附物种的可能性。需要用于干燥颗粒中的时间将取决于该溶剂的蒸气压。 24小时是典型的，但是结果通常是不敏感的等待时间短至12小时和长达3周。 </li></ol></li></ol> 2.漫反射红外光谱测量<ol><li>准备红外光谱仪:调整配件，清洗室<ol><li>打开红外光谱仪。 </li><li>为了准备漫反射红外光谱测量，将漫反射采样附件进入红外光谱仪的采样舱。红外光谱仪可以是任何傅里叶变换能够与漫反射采样装置接口的红外光谱仪。使用Shimadzu IR威望21光谱仪接口与派克科技EasiDiff配件被用于该协议。对于大多数的油墨颗粒，一个标准的氘，L-丙氨酸掺杂三甘氨酸硫酸盐（DLATGS）检测器提供了足够的灵敏度进行测定。液氮冷却的碲镉汞（MCT）Detector提供一个四到灵敏度提高十倍，但是这通常不是必要的用于识别墨粒子表面吸附物。 </li><li>漫反射率采样附件对齐按照制造商的说明。 </li></ol></li><li>调整后，关闭红外采样舱，并开始用氮气或无二氧化碳排放，空气干燥（10升/分钟清除率）清洗。一个标准的帕克Balston的FT-IR吹扫气体发生器提供空气与低于1ppm水和CO 2。的必要，以获得一个稳定的水和CO 2的分类室吹扫时间的量将依赖于样本室配置和湿度在实验室。必要的吹扫时间可通过实验比较的背景光谱采取在1或2分钟的间隔，并评估水的强度和CO 2频带作为时间的函数来确定。 </li><li>准备样品漫反射红外光谱MEASurement <ol><li>获得以下样品制备附件:小（35毫米）玛瑙研钵和杵，小金属刮刀，直刀片，以及两个漫反射红外线的样品杯。擦拭干净，用乙醇配件，然后用丙酮，并允许他们在50℃的烘箱中干燥10分钟。 </li><li>从烤箱中取出清洁，干燥的样品制备配件，将它们放在一个大的Kimwipe，并让他们冷却至室温。 </li><li>同时将样品制备配件冷却，从炉中取出干燥的油墨颗粒，并使用一个分析天平来测量0.025克颗粒样品。离开样品坐在分析天平。 </li><li>返回样品制备配件，倒0.5克KBr压入玛瑙研钵中。始终使用溴化钾售价为红外应用。溴化钾（The​​rmo Scientific）进行的预测个体0.5克包被推荐的，因为它们最小化称量时间和吸湿溴化钾暴露于ambie新台币水蒸气。研磨KBr压到一个统一的外观，通常是1分钟的连续手工研磨的。 </li><li>完全填满漫反射红外线取样杯与地面溴化钾粉末之一。轻轻按下与杵的钝端的粉，顶过采样杯溴化钾。 </li><li>使用剃刀刀片的侧弄平溴化钾的顶部在样品杯中。此填充和平坦化样本是参考或背景。 </li><li>处理任何溴化钾留在砂浆，并擦拭干净。 </li><li>打开溴化钾粉末的新0.5克分组（或者添加0.5克溴化钾粉末），并倒入砂浆。 </li><li>添加预先称重0.025克墨粒子的0.5克溴化钾的，和研磨带杵以形成均匀的粉末，通常为1分钟连续手工研磨。墨粒子与溴化钾该比值提供了测量在5％（重量）的样品。这是标准的范围内（1 - 10重量％），但也可以上下调整取决于ön个样本的吸收率和信号强度。 </li><li>按照步骤2.3.5和2.3.6创建充满颗粒/溴化钾混合物样品杯。 </li></ol></li><li>红外光谱检测<ol><li>放置参考和样品杯插入支架，和保持器放置到漫反射红外光谱采样附件。保持器定位使得包含背景杯（纯溴化钾）材料暴露于红外辐射。 </li><li>关闭红外采样隔室，并允许隔室吹扫5分钟。此吹扫时间可根据所需的时间量确定为必要的，在步骤2.2进行调整。 </li><li> 5分钟后清洗的，得到在所关心的区域中的背景的红外光谱。扫描的次数应设置的信号最大化信噪比，同时尽量减少测量时间。 128扫描在4 -1的分辨率通常是足够的。 </li><li>的背景和经过ð扫描完成时，打开红外样品室和移动包含颗粒/溴化钾混合物使得它现在暴露于红外辐射的杯子。 </li><li>重复步骤2.4.2和2.4.3得到的粒子/溴化钾混合物的光谱。 </li></ol></li></ol>

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作者什么都没有透露。

的两个关键因素的产生高品质的红外光谱使用此过程是:1）最小化水的污染的绝对量和在样品和参比杯之间的水的污染的量的差异;和2）创建样本和参照杯具有均匀平坦层和类似溴化钾晶粒尺寸。这两个因素都受到特别注意在2.3节所列的样品制备程序来实现的。 为了最大限度地减少水的污染的总量，并保持水的污染的参比和样品相同，有必要尽量减少时间，该吸湿溴化钾是在?...

添加剂制造近来成为一个有前途的技术，一切从陶瓷半导体制造医疗器械1。作为添加剂制造的应用扩大到印刷陶瓷，金属氧化物，和金属零件，需要制定专门功能性油墨产生。如何制定所需的功能性油墨的问题涉及到一个根本性的问题，表面和胶体科学:什么是由胶体粒子分散体是稳定的防止聚集的机制？广泛地说，稳定化需要，从而防止颗粒（和因此聚合）的附近的方式或者通过库仑斥力（静电稳定化），由聚合物缠结（空间稳定）的熵惩罚，或由库仑的组合的颗粒表面的变形和熵力（电空间稳定）2。为了实现任何的这些机制稳定化，通常需要通过附着聚合物或较短链的官能团进行修改的粒子表面的化学反应。因此，稳定的功能性油墨的合理配方要求我们知道给定的化学添加剂是否附着到颗粒表面和什么化学基团附着到颗粒表面。 在这个协议中提出的方法的目的是要证明在功能性油墨吸附在颗粒表面的化学物种的快速鉴定。这个目标是从表面和胶体科学家科学家和感兴趣印刷陶瓷，金属氧化物和金属设备工程师的范围广泛的实践活性的专门任务官能油墨制剂跃迁特别重要。实现这一目标，需要设计一种克服表征不透明，高固体负载分散体的挑战的实验。它还需要鉴别通道之间emical物种中存在的分散体，但不吸附在从那些实际吸附的颗粒。它还需要被化学吸附在从那些弱物理吸附的颗粒的那些物种之间进行区分。在这个实验方案，我们提出利用漫反射红外光谱仪对分散剂附着在功能性油墨的特性。漫反射红外光谱测量如下必要区分吸附物质从那些仅仅存在于分散体中的分析前的样品制备技术。 多种方法目前用于洞察化学油墨组分和胶态分散颗粒之间的相互作用的性质。一些这些方法是间接的探针，其中测得特性被假定为关联与表面官能化。例如，改变泥浆流变性或沉淀 - [R阿泰被推定与相关吸附表面改性剂3。粒径分布，作为其特征在于通过动态光散射（DLS），和ζ电位，为特征的电泳迁移率，提供深入了解聚合物或物种的表面电荷4,5的吸附。同样地，采样的质量损失为探测由热重量分析（TGA）涉及解吸物质的存在和被吸附物和粒子6之间的相互作用的强度。从上面提到的间接探针的信息表明改变表面化学性质，但它们不提供直接洞察吸附物种的身份，或它的吸附机理。直接洞察为功能性油墨，其中，大量的部件都存在于分散体特别重要。为了提供更详细的分子水平信息，X射线光电子能谱（XPS）7，13 C核磁振（NMR）4,6，和红外光谱8-12已探索。这三个选项中，红外光谱法是特别有前途。在比较13 C-NMR，红外光谱不需要油墨，分析纯溶剂进行配制，以防止测量13过程中的干扰。相比于X射线光电子能谱，标准红外光谱可以在环境压力下进行，避免了需要在测量过程中超高真空条件。 有文献先例利用红外光谱探测胶态分散陶瓷，金属氧化物，和金属纳米粒子之间的相互作用。这些作品可以分离成尝试使用衰减全反射红外（ATR-IR）的9到测量原位界面化学，并尝试使用固体采样8以测量界面化学易地 。 W¯¯往往微不足道有优势现场测量，出现由于需要进行光谱操作的不确定性使该方法难以用于多组分的油墨，其中有溶剂和多种聚合物组分。因此，该协议侧重于固体取样和易地测量。所有的固体采样方法需要在那里的固体通过从溶剂中分离出的颗粒而得到的前处理步骤，并在红外线测量上的固体颗粒进行的分析步骤。方法之间的不同是在样品前处理的选择和在用于固体的红外分析实验技术的选择。在历史上，传统的方式来使用红外光谱来分析固体含量为研磨少量用溴化钾（KBr压）粉末固体样品的（&lt;1％），然后经受混合物以高压烧结。其结果是透明KBr压片。该公关ocedure已成功地尝试与来自官能化聚乙烯胺10氧化锆纳米粒子的水性悬浮液，用脂肪酸单层钴纳米颗粒7的粉末，并与对Fe 3 O 4纳米颗粒14儿茶酚衍生的分散剂。尽管检测吸附的分散剂的溴化钾造粒技术的这些成功的应用，漫反射红外光谱提供了几个优点。一个优点是简化了样品制备。在对比溴化钾造粒，在漫反射固体样品可以简单地用手工研磨。不存在烧结步骤作为本身被装入样品杯和漫散射的红外光进行测量的粉末。漫反射在KBr压造粒的另一优点是增加的表面灵敏度15。在表面灵敏度的增加是对于本申请特别有用，其中，CRI蒂卡尔问题是存在和吸附物的性质的纳米颗粒的表面上。 在已经使用了漫反射采样技术来探测在胶态分散的样品的化学物质的吸附作品，一次差值出现在从液体介质中分离出纳米颗粒的方法。这个步骤是关键的，因为如果没有分离，这将是不可能区分从分散剂简单地溶解在液体介质中特殊吸附分散剂。在几个实例中，分离的方法，没有从实验方案12,16,17明显。当指定时，最常采用的方法包括重力分离。的理由是，陶瓷，金属氧化物，以及金属纳米颗粒的所有比周围介质更加密集。当他们定居，他们将拖累他们只特异性吸附物种。化学物质不与部分交互icles将留在溶液中。虽然可能分散在正常重力18随手解决，稳定的喷墨油墨不宜observably解决在不到一年的时间。因此，优选采用离心预分析分离的方法。这已被证明在分散剂吸附的几项研究对玻璃微粒19,20，在氧化铝上的8分散剂粘合剂吸附和CuO 11的阴离子分散剂官能化。最近，我们用它来 ​​评估的脂肪酸中使用的固体氧化物燃料电池层21的喷墨和气溶胶喷射印刷的非水氧化镍分散体结合的机制。

<table><tbody><tr><td>FTIR bench</td><td>Shimadzu Scientific Instruments</td><td>IR_Prestige 21 used in this work; in 2013 IR-Tracer 100 model replaced Prestige-21</td><td>Any research grade FTIR with purgable sample compartment is acceptable</td></tr><tr><td>Purge gas generator for sample compartment</td><td>Parker Balston</td><td>74-5041NA Lab Gas Generator</td><td>Provides air with less than 1&amp;nbsp;ppm CO&lt;sub&gt;2&lt;/sub&gt; and water; also possible to purge compartment with N&lt;sub&gt;2&lt;/sub&gt; tank</td></tr><tr><td>Diffuse Reflectance Infrared Accessory</td><td>Pike Technologies</td><td>042-10XX</td><td>Includes sample preparation kit and mortar and pestle (these can also be purchased separately, described below)</td></tr><tr><td>Diffuse Reflectance Sample Preparation kit</td><td>Pike Technologies</td><td>042-3040</td><td>Includes sample holder cups, spatulas, alignment mirror, mirror brush, razor blades</td></tr><tr><td>Agate mortar and pestle</td><td>Pike Technologies</td><td>161-5035</td><td></td></tr><tr><td>Centrifuge</td><td>ThermoScientific</td><td>Sorvall ST16</td><td>Most benchtop centrifuges capable of ~5,000 rpm will be acceptable</td></tr><tr><td colspan="4">[header]</td></tr><tr><td colspan="4">Consumables</td></tr><tr><td>Centrifuge tubes</td><td>Evergreen Scientific</td><td>222-2470-G8K</td><td>Any centrifuge tube of compatible size and material is acceptable</td></tr><tr><td>KBr powder packets</td><td>ThermoScientific</td><td>50-465-317</td><td>Also possible to use alternative KBr supplier</td></tr></tbody></table>

diffuse reflectance infrared spectroscopic identification of dispersant/particle bonding mechanisms in functional inks

In additive manufacturing, or 3D printing, material is deposited drop by drop, to create micron to macroscale layers. A typical inkjet ink is a colloidal dispersion containing approximately ten components including solvent, the nano to micron scale particles which will comprise the printed layer, polymeric dispersants to stabilize the particles, and polymers to tune layer strength, surface tension and viscosity. To rationally and efficiently formulate such an ink, it is crucial to know how the components interact. Specifically, which polymers bond to the particle surfaces and how are they attached? Answering this question requires an experimental procedure that discriminates between polymer adsorbed on the particles and free polymer. Further, the method must provide details about how the functional groups of the polymer interact with the particle. In this protocol, we show how to employ centrifugation to separate particles with adsorbed polymer from the rest of the ink, prepare the separated samples for spectroscopic measurement, and use Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS) for accurate determination of dispersant/particle bonding mechanisms. A significant advantage of this methodology is that it provides high level mechanistic detail using only simple, commonly available laboratory equipment. This makes crucial data available to almost any formulation laboratory. The method is most useful for inks composed of metal, ceramic, and metal oxide particles in the range of 100 nm or greater. Because of the density and particle size of these inks, they are readily separable with centrifugation. Further, the spectroscopic signatures of such particles are easy to distinguish from absorbed polymer. The primary limitation of this technique is that the spectroscopy is performed ex-situ on the separated and dried particles as opposed to the particles in dispersion. However, results from attenuated total reflectance spectra of the wet separated particles provide evidence for the validity of the DRIFTS measurement.

在这个协议中所述的实验步骤已应用于洞察的NiO颗粒稳定的机制中用于打印的固体氧化物燃料电池的阳极的油墨。这种油墨是氧化镍粒子在2-丁醇，α-萜品醇，和一系列分散剂和粘合剂22中的分散体。代表性的结果示此处的NiO在2-丁醇的简化分散用油酸分散剂。在图1A中，我们表明生漫反射红外光谱数据。为了解释该数据，有必要比较之前分散体（ 图1B）从分散到?...

Watch this Scientific Journal Video about Diffuse Reflectance Infrared Spectroscopic Identification of Dispersant/Particle Bonding Mechanisms in Functional Inks at JoVE.com

Diffuse Reflectance Infrared Spectroscopic Identification of Dispersant/Particle Bonding Mechanisms in Functional Inks

Formulation of stable, functional inks is critical to expanding the applications of additive manufacturing. In turn, knowledge of the mechanisms of dispersant/particle bonding is required for effective ink formulation. Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS) is presented as a simple, inexpensive way to gain insight into these mechanisms.

弥漫分散剂/粒子绑定机制反射红外光谱鉴定功能性油墨

In additive manufacturing, or 3D printing, material is deposited drop by drop, to create micron to macroscale layers.  A typical inkjet ink is a colloidal ...

diffuse-reflectance-infrared-spectroscopic-identification

Research

JoVE Journal

Chemistry

13.6K 次观看.  New York City College of Technology, City University of New York (CUNY). Formulation of stable, functional inks is critical to expanding the applications of additive manufacturing. In turn, knowledge of the mechanisms of dispersant/particle bonding is required for effective ink formulation. Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS) is presented as a simple, inexpensive way to gain insight into these mechanisms.

视频: Diffuse Reflectance Infrared Spectroscopic Identification of Dispersant/Particle Bonding Mechanisms in Functional Inks

Polymer Microarrays for High Throughput Discovery of Biomaterials

The discovery of novel biomaterials that are optimized for a specific biological application is readily achieved using polymer microarrays, which allows a combinatorial library of materials to be screened in a parallel, high throughput format1. Herein is described the formation and characterization of a polymer microarray using an on-chip photopolymerization technique 2. This involves mixing monomers at varied ratios to produce a library of monomer solutions, transferring the solution to a glass slide format using a robotic printing device and curing with UV irradiation. This format is readily amenable to many biological assays, including stem cell attachment and proliferation, cell sorting and low bacterial adhesion, allowing the ready identification of 'hit' materials that fulfill a specific biological criterion3-5. Furthermore, the use of high throughput surface characterization (HTSC) allows the biological performance to be correlated with physio-chemical properties, hence elucidating the biological-material interaction6. HTSC makes use of water contact angle (WCA) measurements, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). In particular, ToF-SIMS provides a chemically rich analysis of the sample that can be used to correlate the cell response with a molecular moiety. In some cases, the biological performance can be predicted from the ToF-SIMS spectra, demonstrating the chemical dependence of a biological-material interaction, and informing the development of hit materials5,3.

A description of the formation of a polymer microarray using an on-chip photopolymerization technique. The high throughput surface characterization using atomic force microscopy, water contact angle measurements, X-ray photoelectron spectroscopy and time of flight secondary ion mass spectrometry and a cell attachment assay is also described.

聚合物芯片高通量发现的生物材料

The discovery of novel biomaterials that are optimized for a specific biological application is readily achieved using polymer microarrays, which allows a ...

科研

生物工程

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

超分子胶体的合成与表征

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

化学

Controlled Synthesis and Fluorescence Tracking of Highly Uniform Poly(N-isopropylacrylamide) Microgels

Stimuli-sensitive poly(N-isopropylacrylamide) (PNIPAM) microgels have various prospective practical applications and uses in fundamental research. In this work, we use single particle tracking of fluorescently labeled PNIPAM microgels as a showcase for tuning microgel size by a rapid non-stirred precipitation polymerization procedure. This approach is well suited for prototyping new reaction compositions and conditions or for applications that do not require large amounts of product. Microgel synthesis, particle size and structure determination by dynamic and static light scattering are detailed in the protocol. It is shown that the addition of functional comonomers can have a large influence on the particle nucleation and structure. Single particle tracking by wide-field fluorescence microscopy allows for an investigation of the diffusion of labeled tracer microgels in a concentrated matrix of non-labeled microgels, a system not easily investigated by other methods such as dynamic light scattering.

Controlled Synthesis and Fluorescence Tracking of Highly Uniform PolyN-isopropylacrylamide Microgels

Non-stirred precipitation polymerization provides a rapid, reproducible prototyping approach to the synthesis of stimuli-sensitive poly(N-isopropylacrylamide) microgels of narrow size distribution. In this protocol synthesis, light scattering characterization and single particle fluorescence tracking of these microgels in a wide-field microscopy setup are demonstrated.

可控合成和高度统一聚荧光追踪（<em&gt;ñ</em&gt; -isopropylacrylamide）微凝胶

Stimuli-sensitive poly(N-isopropylacrylamide) (PNIPAM) microgels have various prospective practical applications and uses in fundamental research. In this ...

Inkjet-printed Polyvinyl Alcohol Multilayers

Inkjet printing is a modern method for polymer processing, and in this work, we demonstrate that this technology is capable of producing polyvinyl alcohol (PVOH) multilayer structures. A polyvinyl alcohol aqueous solution was formulated. The intrinsic properties of the ink, such as surface tension, viscosity, pH, and time stability, were investigated. The PVOH-based ink was a neutral solution (pH 6.7) with a surface tension of 39.3 mN/m and a viscosity of 7.5 cP. The ink displayed pseudoplastic (non-Newtonian shear thinning) behavior at low shear rates, and overall, it demonstrated good time stability. The wettability of the ink on different substrates was investigated, and glass was identified as the most suitable substrate in this particular case. A proprietary 3D inkjet printer was employed to manufacture polymer multilayer structures. The morphology, surface profile, and thickness uniformity of inkjet-printed multilayers were evaluated via optical microscopy.

An inkjet printer was used to manufacture polyvinyl alcohol multilayers. Polyvinyl alcohol water-based ink was formulated, and the main physical properties were investigated.

喷墨印刷聚乙烯醇多层

Inkjet printing is a modern method for polymer processing, and in this work, we demonstrate that this technology is capable of producing polyvinyl alcohol ...

工程学

A Two-Step Pyrolysis-Gas Chromatography Method with Mass Spectrometric Detection for Identification of Tattoo Ink Ingredients and Counterfeit Products

Tattoo inks are complex mixtures of ingredients. Each of them possesses different chemical properties which have to be addressed upon chemical analysis. In this method for two-step pyrolysis online coupled to gas chromatography mass spectrometry (py-GC-MS) volatile compounds are analyzed during a first desorption run. In the second run, the same dried sample is pyrolyzed for analysis of non-volatile compounds such as pigments and polymers. These can be identified by their specific decomposition patterns. Additionally, this method can be used to differentiate original from counterfeit inks. Easy screening methods for data evaluation using the average mass spectra and self-made pyrolysis libraries are applied to speed up substance identification. Using specialized evaluation software for pyrolysis GS-MS data, a fast and reliable comparison of the full chromatogram can be achieved. Since GC-MS is used as separation technique, the method is limited to volatile substances upon desorption and after pyrolysis of the sample. The method can be applied for quick substance screening in market control surveys since it requires no sample preparation steps.

This method for two-step pyrolysis online coupled to gas chromatography with mass spectrometric detection and data evaluation protocol can be used for multi-component analysis of tattoo inks and discrimination of counterfeit products.

一种用于检测纹身油墨成分和假冒产品的两步热解-气相色谱法

Tattoo inks are complex mixtures of ingredients. Each of them possesses different chemical properties which have to be addressed upon chemical analysis. ...

In situ FTIR Spectroscopy as a Tool for Investigation of Gas/Solid Interaction: Water-Enhanced CO2 Adsorption in UiO-66 Metal-Organic Framework

In situ infrared spectroscopy is an inexpensive, highly sensitive, and selective valuable tool to investigate the interaction of polycrystalline solids with adsorbates. Vibrational spectra provide information on the chemical nature of adsorbed species and their structure. Thus, they are very useful for obtaining molecular level understanding of surface species. The IR spectrum of the sample itself gives some direct information about the material. General conclusions can be drawn concerning hydroxyl groups, some stable surface species and impurities. However, the spectrum of the sample is &#34;blind&#34; with respect to the presence of coordinatively unsaturated ions and gives rather poor information about the acidity of surface hydroxyls, species decisive for the adsorption and catalytic properties of the materials. Furthermore, no discrimination between bulk and surface species can be made. These problems are solved by the use of probe molecules, substances that interact specifically with the surface; the alteration of some spectral features of these molecules as a result of adsorption provides valuable information about the nature, properties, location, concentration, etc., of the surface sites.
The experimental protocol for in-situ IR studies of gas/sample interaction includes preparation of a sample pellet, activation of the material, initial spectral characterization through the analysis of the background spectra, characterization by probe molecules, and study of the interaction with a particular set of gas mixtures. In this paper we investigate a zirconium terephthalate metal organic framework, Zr6O4(OH)4(BDC)6 (BDC = benzene-1,4-dicarboxylate), namely UiO-66 (UiO refers to University of Oslo). The acid sites of the UiO-66 sample are determined by using CO and CD3CN as molecular probes. Furthermore, we have demonstrated that CO2 is adsorbed on basic sites exposed on dehydroxylated UiO-66. Introduction of water to the system produces hydroxyl groups acting as additional CO2 adsorption sites. As a result, CO2 adsorption capacity of the sample is strongly enhanced.

In situ FTIR Spectroscopy as a Tool for Investigation of Gas/Solid Interaction: Water-Enhanced CO2 Adsorption in UiO-66 Metal-Organic Framework

The use of FTIR spectroscopy for investigation of the surface properties of polycrystalline solids is described. Preparation of sample pellets, activation procedures, characterization with probe molecules and model studies of CO2 adsorption are discussed.

原位FTIR 光谱作为气体/固体相互作用研究工具:UiO-66 金属-有机框架中的水增强 CO2吸附

In situ infrared spectroscopy is an inexpensive, highly sensitive, and selective valuable tool to investigate the interaction of polycrystalline solids ...

Separation and Identification of Conventional Microplastics from Farmland Soils

Microplastics (MPs) pollution in the terrestrial environment has received increasing attention over the last decade, with increasing studies describing the numbers and types of MPs in different soil systems and their impacts on soil and crop health. However, different MPs extraction and analytical methods are used, limiting opportunities to compare results and generate reliable evidence for industry advice and policymakers. Here, we present a protocol that describes the methodology for sampling, separation, and chemical identification of conventional MPs&#160;from soil. The method is low-cost, and the materials are readily available. This enhances operational ease and may help with widespread adoption. The protocol provides detailed information on sample collection from the top 0-30 cm of soil using plastic-free utensils; simulation of different soil types through the use of various solid media (such as bentonite clay, silicon dioxide, and non-contaminated soil), with the addition of the same mass&#160;of polyethylene(PE)-MPs for subsequent quantification; density separation of plastic particles utilizing saturated sodium chloride (NaCl) solution and digestion of organic impurities in the supernatant using 4 M sodium hydroxide (NaOH) solution; quantification of particles using fluorescent microscopy after Nile Red staining; and polymer identification using micro&#160;Fourier-Transform Infrared Spectroscopy (&#956;-FTIR) or Laser-Direct Infrared (LDIR) spectroscopy. The MPs recovery rate ranged from 83% - 90% for the abovementioned media. This protocol presents an efficient method for soil MPs analysis that is optimized for feasibility, applicability, and cost-effectiveness. Moreover, the video accompanied can guide the process of analyzing the soil MPs step-by-step virtually. This study is dedicated to standardizing the methods for soil MPs analysis, enhancing the connectivity and comparability of measurements, and establishing a foundation for more standardized and scientific research.

Presented here is a method for extracting microplastics from soil and identifying their polymer types. The method has been optimized for execution, applicability, and cost-effectiveness. It lays a scientific foundation for standardizing the analytical method to identify microplastics in soils.

农田土壤中常规微塑料的分离和鉴定

Microplastics (MPs) pollution in the terrestrial environment has received increasing attention over the last decade, with increasing studies describing ...

环境科学

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization

3D printing provides facile access to geometrically complex materials. However, these materials have intrinsically linked bulk and interfacial properties dependent on the chemical composition of the resin. In the current work, 3D printed materials are post-functionalized using the 3D printer hardware via a secondary surface-initiated polymerization process, thus providing independent control over the bulk and interfacial material properties. This process begins with preparing liquid resins, which contain a monofunctional monomer, a crosslinking multifunctional monomer, a photochemically labile species that enables initiation of polymerization, and critically, a thiocarbonylthio compound which facilitates reversible addition-fragmentation chain transfer (RAFT) polymerization. The thiocarbonylthio compound, known commonly as a RAFT agent, mediates the chain growth polymerization process and provides polymeric materials with more homogeneous network structures. The liquid resin is cured in a layer-by-layer fashion using a commercially available digital light processing 3D printer to give three-dimensional materials having spatially controlled geometries. The initial resin is removed and replaced with a new mixture containing functional monomers and photoinitiating species. The 3D printed material is then exposed to light from the 3D printer in the presence of the new functional monomer mixture. This allows photoinduced surface-initiated polymerization to occur from the latent RAFT agent groups on the surface of the 3D printed material. Given the chemical flexibility of both resins, this process allows a wide range of 3D printed materials to be produced with tailorable bulk and interfacial properties.

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization

The present protocol describes the digital light processing-based 3D printing of polymeric materials using type I photoinitiated reversible addition-fragmentation chain transfer polymerization and the subsequent in situ material post-functionalization via surface-mediated polymerization. Photoinduced 3D printing provides materials with independently tailored and spatially controlled bulk and interfacial properties.

通过I型光引发可逆加成-碎片链转移聚合进行3D打印和原位表面改性

3D printing provides facile access to geometrically complex materials. However, these materials have intrinsically linked bulk and interfacial properties ...

通过纳米级红外光谱探索多相聚合物系统

Advances in Nanoscale Infrared Spectroscopy to Explore Multiphase Polymeric Systems

Multiphase polymeric systems encompass local domains with dimensions that can vary from a few tens of nanometers to several micrometers. Their composition is commonly assessed using infrared spectroscopy, which provides an average fingerprint of the various materials contained in the volume probed. However, this approach does not offer any details on the arrangement of the phases in the material. Interfacial regions between two polymeric phases, often in the nanoscale range, are also challenging to access. Photothermal nanoscale infrared spectroscopy monitors the local response of materials excited by infrared light with the sensitive probe of an atomic force microscope (AFM). While the technique is suitable for interrogating small features, such as individual proteins on pristine gold surfaces, the characterization of three-dimensional multicomponent materials is more elusive. This is due to a relatively large volume of material undergoing photothermal expansion, defined by the laser focalization onto the sample and by the thermal properties of the polymeric constituents, compared to the nanoscale region probed by the AFM tip. Using a polystyrene (PS) bead and a polyvinyl alcohol (PVA) film, we evaluate the spatial footprint of photothermal nanoscale infrared spectroscopy for surface analysis as a function of the position of PS in the PVA film. The effect of the feature position on the nanoscale infrared images is investigated, and spectra are acquired. Some perspectives on the future advances in the field of photothermal nanoscale infrared spectroscopy are provided, considering the characterization of complex systems with embedded polymeric structures.

作者聚焦:探索多相聚合物系统的纳米级红外光谱进展  

This protocol describes the application of atomic force microscopy and nanoscale infrared spectroscopy to evaluate the performance of photothermal nanoscale infrared spectroscopy in the characterization of three-dimensional multi-polymeric samples.

纳米级红外光谱探索多相聚合物体系的进展

Multiphase polymeric systems encompass local domains with dimensions that can vary from a few tens of nanometers to several micrometers. Their composition ...

弥漫分散剂/粒子绑定机制反射红外光谱鉴定功能性油墨

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通过I型光引发可逆加成-碎片链转移聚合进行3D打印和原位表面改性

纳米级红外光谱探索多相聚合物体系的进展

纳米级红外光谱探索多相聚合物体系的进展