Because of the biological importance of thiols, the development of probes for thiols has been an active research area in recent years. In this review, we summarize the results of recent exciting reports regarding thiol-addition reactions and their applications in thiol recognition. The examples reported can be classified into four reaction types including 1,1, 1,2, 1,3, 1,4 addition reactions, according to their addition mechanisms, based on different Michael acceptors. In all cases, the reactions are coupled to color and/or emission changes, although some examples dealing with electrochemical recognition have also been included. The use of thiol-addition reactions is a very simple and straightforward procedure for the preparation of thiol-sensing probes.

Understanding the pathological process of biological systems can greatly improve the prevention and treatment of diseases. The study of pathological processes has now reached the molecular level, and molecular fluorescent probes have become a powerful tool. Chromene, also known as benzo-pyran molecule, is a structural element of natural products with good biological compatibility and was developed as a fluorescent probe. The thiol−chromene "click" nucleophilic pyran ring-opening reaction allows the quick detection of thiol. In this work, the chromene alcohol can function as an efficient self-immolative spacer, which covalently links NIR fluorophore via a carbonyl ester. Due to its favorable characteristics and superior applicability, the self-immolative amplifier NIR-HMPC achieves the specific, rapid, sensitive, NIR fluorescent detection of thiols. Furthermore, the indoles iodized salt in the system can specifically target thiols in mitochondria. Thus, this probe was used to visualize the fluctuations of thiols during oxidative stress and cell apoptosis, cerebral ischemia reperfusion, demonstrating that it is valuable for elucidating pathophysiology process in living organism. This discovery provides an effective means for studying the pathological process of thiol related diseases.

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An ultraviolet-visible light (UV-Vis)-reversible but fluorescence-irreversible chemosensor was developed for the detection of copper. Coordination between the probe, 2-pyridylaldehyde fluorescein hydrazone (FHP), and Cu(2+) gave a reversible UV-Vis response, Storage of the probe-Cu complex resulted in hydrolytic cleavage of the N═C bond, which released the fluorophore (ring-opened fluorescein hydrazine) and gave irreversible fluorescence. Thus, FHP becomes a multifunctional chemosensor, and its reversibility can be controlled by the reaction time. Cu(2+) in living cells could be detected using FHP and general fluorescence methods.

We have used friction force microscopy to study the effects of adhesion on the boundary friction of self-assembled monolayers of the aromatic compounds thiophenol, p-phenylthiophenol, p-terphenyl thiol, 2-naphthalenethiol, and benzyl mercaptan on gold. To control the adhesion between the monolayer-covered tip and substrate, the friction measurements were made in dry N(2) gas or in ethanol. At low loads, low adhesion (in ethanol) resulted in a linear dependence of the friction force on load (i.e., F = muL) whereas higher adhesion between the same monolayers (in N(2)) gave an apparent area-dependent friction. The friction in the adhesive systems was well described by F = S(c)A with the contact area, A, calculated for a thin, linearly elastic film confined between rigid substrates using the thin-coating contact mechanics (TCCM) model in a transition regime between its DMT- and JKR-like limits. With increasing packing density of the monolayers, a systematic decrease was found in the friction coefficient (mu) obtained in ethanol and the critical shear stress (S(c)) obtained in N(2). To describe these aromatic monolayers with the extended TCCM model, a higher Young's modulus was neeeded than for fatty acid monolayers of similar packing density.

Summary Protein arginine methylation regulates multiple biological processes. Deregulation of protein arginine methyltransferase (PRMT) activities has been observed in many disease phenotypes. Small molecule probes that target PRMTs with strong affinity and selectivity can be used as valuable tools to dissect biological mechanisms of arginine methylation and establish the role of PRMT proteins in a disease process. In this work, we report synthesis and evaluation of a class of carbocyanine compounds containing indolium, benz[e]indolium or benz[c,d]indolium heterocyclic moieties that bind to the predominant arginine methyltransferase PRMT1 and inhibit its methyltransferase activity at low micromolar potencies. In particular, the developed molecules have long wavelength colorimetric and fluorometric photoactivities, which can be used for optical and near-infrared fluorescence imaging in cells or biological tissues. Together, these new chemical probes have potential application in PRMT studies both as enzyme inhibitors and as fluorescent dyes for microscope imaging.

A regenerative, molecular machine-like "ON-OFF-ON" chemosensor based on a chromene molecule with the pyran ring "OFF-ON-OFF" cycle is reported for the first time. It behaves as a molecular lock that requires a thiol "key" to open the lock and a mercury(II) ion "hand" that unlatches the key for unsheathing the key to close the lock.

We have studied the frictional properties of self-assembled monolayers (SAMs) of phenyl-terminated alkanethiols, C 6 H 5 (CH 2 ) n SH (n = 13-16) on template-stripped gold. The friction force was measured with atomic force microscopy (AFM), and the magnitude of the adhesion was controlled by immersing the sliding contact in ethanol (giving low adhesion) or dry N 2 gas (giving enhanced adhesion relative to ethanol). We observed a linear friction force as a function of load (F = μL) in the systems with low adhesion and a non-linear friction force when the adhesion was higher. The non-linear behavior in the adhesive systems appeared to be area-dependent (F = S c A) and was compared to contact areas calculated using the extended Thin-Coating Contact Mechanics (TCCM) model. In ethanol, the coefficient of friction μ was found to be systematically higher for odd values of n (i.e., for the monolayers in which the terminal phenyl group was oriented closer to the surface normal).