盐酸和氯化钙混合溶液中滴加碳酸钠溶液pH变化的实验探究*

盐酸、氯化钙混合溶液中滴加碳酸钠溶液,当碳酸钙沉淀出现后,混合溶液pH是否基本不变？此时的pH是否为7？为此用数字化实验对盐酸、氯化钙混合溶液中滴加碳酸钠溶液pH的变化进行了探讨,对平台段的出现及平台段溶液pH进行了实验探究和理论分析。     

Extracellular matrix alterations in low‐grade lung adenocarcinoma compared with normal lung tissue by imaging mass spectrometry

Lung adenocarcinoma (LUAD) is the second most common cancer, affecting both men and women. Fibrosis is a hallmark of LUAD occurring throughout progression with excess production of extracellular matrix (ECM) components that lead to metastatic cell processes. Understanding the ECM cues that drive LUAD progression has been limited due to a lack of tools that can access and report on ECM components within the complex tumor microenvironment. Here, we test whether low‐grade LUAD can be distinguished from normal lung tissue using a novel ECM imaging mass spectrometry (ECM IMS) approach. ECM IMS analysis of a tissue microarray with 20 low‐grade LUAD tissues and 20 normal lung samples from 10 patients revealed 25 peptides that could discriminate between normal and low‐grade LUAD using area under the receiver‐operating curve (AUC) ≥0.7, P value ≤.001. Principal component analysis demonstrated that 62.4% of the variance could be explained by sample origin from normal or low‐grade tumor tissue. Additional work performed on a wedge resection with moderately differentiated LUAD demonstrated that the ECM IMS analytical approach could distinguish LUAD spectral features from spectral features of normal adjacent lung tissue. Conventional liquid chromatography with tandem mass spectrometry (LC‐MS/MS) proteomics demonstrated that specific sites of hydroxylation of proline (HYP) were a main collagen post translational modification that was readily detected in LUAD. A distinct peptide from collagen 3A1 modified by HYP was increased 3.5 fold in low‐grade LUAD compared with normal lung tissue (AUC 0.914, P value <.001). This suggests that regulation of collagen proline hydroxylation could be an important process during early LUAD fibrotic deposition. ECM IMS is a useful tool that may be used to define fibrotic deposition in low‐grade LUAD.     

Direct Evidence of Local pH Change and the Role of Alkali Cation during CO2 Electroreduction in Aqueous Media

We report, for the first time, utilizing a rotating ring‐disc electrode (RRDE) assembly for detecting changes in the local pH during aqueous CO₂ reduction reaction (CO₂RR). Using Au as a model catalyst where CO is the only product, we show that the CO oxidation peak shifts by ?86±2 mV/pH during CO₂RR, which can be used to directly quantify the change in the local pH near the catalyst surface during electrolysis. We then applied this methodology to investigate the role of cations in affecting the local pH during CO₂RR and find that during CO₂RR to CO on Au in an MHCO₃ buffer (where M is an alkali metal), the experimentally measured local basicity decreased in the order Li⁺ > Na⁺ > K⁺ > Cs⁺, which agreed with an earlier theoretical prediction by Singh et al. Our results also reveal that the formation of CO is independent of the cation. In summary, RRDE is a versatile tool for detecting local pH change over a diverse range of CO₂RR catalysts. Additionally, using the product itself (i.e. CO) as the local pH probe allows us to investigate CO₂RR without the interference of additional probe molecules introduced to the system. Most importantly, considering that most CO₂RR products have pH‐dependent oxidation, RRDE can be a powerful tool for determining the local pH and correlating the local pH to reaction selectivity.     

Biocompatible and pH‐Responsive Colloidal Surfactants with Tunable Shape for Controlled Interfacial Curvature

Molecular‐surfactant‐stabilized emulsions are susceptible to coalescence and Ostwald ripening. Amphiphilic particles, which have a much stronger anchoring strength at the interface, could effectively alleviate these problems to form stable Pickering emulsions. Herein, we describe a versatile method to fabricate biocompatible amphiphilic dimer particles through controlled coprecipitation and phase separation. The dimer particles consist of a hydrophobic PLA bulb and a hydrophilic shellac–PEG bulb, thus resembling nonionic molecular surfactants. The size and diameter ratio of the dimer particles are readily tunable, providing flexible control over the water/oil interfacial curvature and thus the type of emulsion. The particle‐stabilized emulsions were stable for a long period of time and could be destabilized through a pH‐triggered response. The biocompatible amphiphilic dimer particles with tunable morphology and functionality are thus ideal colloidal surfactants for various applications.     

An Adjustable pH‐Responsive Drug Delivery System Based on Self‐Assembly Polypeptide‐Modified Mesoporous Silica

In this study, an adjustable pH‐responsive drug delivery system using mesoporous silica nanoparticles (MSNs) as the host materials and the modified polypeptides as the nanovalves is reported. Since the polypeptide can self‐assemble via electrostatic interaction at pH 7.4 and be disassembled by pH changes, the modified poly(l ‐lysine) and poly(l ‐glutamate) are utilized for pore blocking and opening in the study. Poly(l ‐lysine)‐MSN (PLL‐MSN) and poly(l ‐glutamate)‐MSN (PLG‐MSN) are synthesized via the ring opening polymerization of N‐carboxyanhydrides onto the surface of mesoporous silica nanoparticles. The successful modification of the polypeptide on MSN is proved by Zeta potential change, X‐ray photoelectron spectroscopy (XPS), solid state NMR, and MALDI‐TOF MS. In vitro simulated dye release studies show that PLL‐MSN and PLG‐MSN can successfully load the dye molecules. The release study shows that the controlled release can be constructed at different pH by adjusting the ratio of PLL‐MSN to PLG‐MSN. Cellular uptake study indicates that the drug is detected in both cytoplasm and nucleus, especially in the nucleus. In vitro cytotoxicity assay indicates that DOX loaded mixture nanoparticles (ratio of PLL‐MSN to PLG‐MSN is 1:1) can be triggered for drug release in HeLa cells, resulting in 88% of cell killing.     

pH‐Switchable Bioelectrocatalysis Based on Weak Polyelectrolyte Multilayers

Weak polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) were assembled into {PAH/PAA}_n layer‐by‐layer films on electrodes. The cyclic voltammetry (CV) response of ferrocenecarboxylic acid (Fc(COOH)) at {PAH/PAA}₅ film electrodes assembled under the specific condition showed pH‐sensitive “on‐off” switching property. This property was further used to control the electrocatalytic oxidation of glucose by glucose oxidase (GOD) with Fc(COOH) as the electron transfer mediator, so that the pH‐switchable bioelectrocatalysis could be realized. The mechanism of pH‐sensitive behavior of the system was explored and believed to originate from the pH‐dependent structure change of the films.     

Responses of Metalloporphyrin‐Based Ion‐Selective Electrodes to pH

The ISEs based on [M(tpp)Cl] (M: Al, Ga, In, Mn, Fe; H₂tpp: tetraphenylporphin) had pH responses across their respective pH ranges, which had some correlation with the pH ranges of the two‐phase hydrolysis. Such pH responses are ascribed to the phase boundary potentials relating to the acid‐base pairs of [M(tpp)(H₂O)]⁺ and [M(tpp)(OH)] and/or [M₂(tpp)₂O]. The potential responses of the In and Fe complexes had the upper limitation to pH of 90 % hydrolysis, whereas those of the Al and Ga complexes had the extension to at least pH 12, indicating stable existence of [M(tpp)(H₂O)]⁺ even in contact with strongly alkaline solutions.     

A New pH Sensor Based on a Glassy Carbon Electrode Coated with a Co/Al Layered Double Hydroxide

A glassy carbon electrode has been coated by electrodeposition with a thin film of cobalt based layered double hydroxide (LDH) and used as a pH sensor. The developed electrode displays a linear super‐Nernstian response (?76.2±0.6 mV/pH) in the pH range between 2 and 14 and it is particularly suitable to operate in strongly alkaline solution. The reproducibility of the sensor construction is good with a relative standard deviation of the calibration curve slopes of±2.5 % (n=4). The electrode has a response time comparable to that exhibited by commercial glass electrodes in the pH range examined and is not affected by interference from the most common anions and cations.     

Nanomotors Sense Local Physicochemical Heterogeneities in Tumor Microenvironments**

The invasion of cancer is brought about by continuous interaction of malignant cells with their surrounding tissue microenvironment. Investigating the remodeling of local extracellular matrix (ECM) by invading cells can thus provide fundamental insights into the dynamics of cancer progression. In this paper, we use an active untethered nanomechanical tool, realized as magnetically driven nanomotors, to locally probe a 3D tissue culture environment. We observed that nanomotors preferentially adhere to the cancer-proximal ECM and magnitude of the adhesive force increased with cell lines of higher metastatic ability. We experimentally confirmed that sialic acid linkage specific to cancer-secreted ECM makes it differently charged, which causes this adhesion. In an assay consisting of both cancerous and non-cancerous epithelia, that mimics the in vivo histopathological milieu of a malignant breast tumor, we find that nanomotors preferentially decorate the region around the cancer cells.     

联合动静态图像分析技术研究鳄鱼血红细胞形态功能随pH值的变化

采用多维显微成像技术,结合有关动、静态图像分析方法,通过测定鳄鱼血红细胞在不同pH值下其形态参数(包括红细胞的接触面积、周长、长轴、短轴、伸长率和圆度)和反映细胞变形能力的频颤变化,揭示了鳄鱼血红细胞形态结构与有关生理功能随环境pH值的变化情况.结果表明,鳄鱼红细胞无论形态结构还是变形能力都比人体的红细胞更耐受酸性环境...