Scaling in reverse osmosis facilities, boilers, heat exchangers, evaporation plants, and oilfield applications is a serious problem worldwide. In order to provide a new insight into the mechanism of the scale formation and inhibition, a novel fluorescent‐tagged bisphosphonate scale inhibitor 1‐hydroxy‐7‐(6‐methoxy‐1,3‐dioxo‐1H‐benzo[de]isoquinolin‐2(3H)‐yl)heptane‐1,1‐diyl‐di(phosphonic acid), (HEDP−F) was synthesized and used for fluorescent microscope visualization of gypsum crystal formation in supersaturated aqueous solutions. The visualization of HEDP−F location on gypsum crystals has demonstrated that the bisphosphonate molecules do not act as they are expected to do according to the current scale inhibition theory. At ambient temperature the gypsum macrocrystals are found to form, and then to grow without visible sorption of bisphosphonate on the crystal edges or any other gypsum crystal growth centers. A tentative nonconventional mechanism of scale inhibition in the bulk supersaturated aqueous solutions of gypsum is proposed.

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The two fluorescent monomers N‐allyl‐4‐methoxy‐1,8‐naphtalimide (F1) and N‐allyl‐2‐(6‐hydroxy‐3‐oxo‐3H‐xanthen‐9‐yl)benzamide (N‐allylamidefluorescein, F2) have been synthesized and then conjugated to either polyacrylate (PAA) or to a co‐polymer of fumaric and acrylic acids (MA‐AA) to give four novel fluorescent‐tagged antiscalants: nonbiodegradable PAA‐F1, PAA‐F2 and biodegradable MA‐AA‐F1, MA‐AA‐F2. All four reagents demonstrate the fluorescence intensity suitable for inhibitors monitoring with a detection limit within 0.40 mg dm−3. A good linear relationship between antiscalant fluorescent intensity and its dosage is detected. PAA‐F1, PAA‐F2, MA‐AA‐F1, and MA‐AA‐F2 can be used for corresponding scale inhibitor content on‐line measurement. For some antiscalants, the fluorescence is found to be dependent on the background heavy metal ions normally present in the cooling water. This effect is explained by the corresponding complexes formation. PAA‐F1, PAA‐F2, MA‐AA‐F1, and MA‐AA‐F2 revealed a good antiscaling activity toward CaCO3 and CaSO4 deposition, comparable with that one of commercial polyacrylates. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45017.

Gypsum scaling in reverse osmosis (RO) desalination process is studied in presence of a novel fluorescent 1,8-naphthalimide-tagged polyacrylate (PAA-F1) by fluorescent microscopy, scanning electron microscopy (SEM), dynamic light scattering (DLS) and a particle counter technique. A comparison of PAA-F1 with a previously reported fluorescent bisphosphonate HEDP-F revealed a better PAA-F1 efficacy, and a similar behavior of polyacrylate and bisphosphonate inhibitors under the same RO experimental conditions. Despite expectations, PAA-F1 does not interact with gypsum. For both reagents, it is found that scaling takes place in the bulk retentate phase via heterogeneous nucleation step. The background "nanodust" plays a key role as a gypsum nucleation center. Contrary to popular belief, an antiscalant interacts with "nanodust" particles, isolating them from calcium and sulfate ions sorption. Therefore, the number of gypsum nucleation centers is reduced, and in turn, the overall scaling rate is diminished. It is also shown that, the scale formation scenario changes from the bulk medium, in the beginning, to the sediment crystals growth on the membrane surface, at the end of the desalination process. It is demonstrated that the fluorescent-tagged antiscalants may become very powerful tools in membrane scaling inhibition studies.However, in spite of numerous relevant studies, some controversy regarding both the dominant scaling mechanism in particular situations and the mechanism of antiscalant activity still exists [12][13][14][15][16][17][18]. Recent reviews on scale formation control in RO technologies [6,19] mention two main hypothetic mechanisms of inhibition: (i) antiscalant molecules adsorb on the active growth sites at the crystal surface of sparingly soluble inorganic salt and retard nucleation and crystal growth by distorting its crystal structure; (ii) antiscalant molecules provide similar electrostatic charge, and thus, repulsion between particles prevents them from agglomeration.Nevertheless, our recent static [20,21] and RO [22] experiments operating gypsum as a model scale in presence of a novel fluorescent-tagged bisphosphonate antiscalant 1-hydroxy-7-(6-methoxy-1,3dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)heptane-1,1-diyl-bis(phosphonic acid), HEDP-F (H 4 hedp-F) revealed a paradoxical effect: an antiscalant does not interact with gypsum at all, but provides nevertheless retardation of corresponding deposit formation. According to the classical crystallization theory [23], this is possible only in the case, when gypsum passes bulk heterogeneous nucleation, and exactly the "nanodust" plays the role of the solid phase template. Indeed, it is demonstrated that HEDP-F molecules being immersed into the stock solution (undersaturated against gypsum) occupy a significant part of "nanodust" crystallization centers and form there their own solid phase Ca 2 hedp-F·nH 2 O. However, polyacrylates are much less sensitive to calcium environment than phosphonates [20,21]. In this way, it was reasonable to study the trace...

The beginning of the 21st century was marked by the intensive development of fiber‐optic sensors. New functional materials with excellent sensory properties are required to design such sensors. Fluorescent probes for neutral and charged molecules are constantly developing. However, only a small part of the reported probes was successfully converted into functional sensing polymers and found real‐world applications. A great challenge is to retain the sensing properties of a probe in a polymer matrix. The purpose of this review is to understand how properties of a probe are changed upon incorporation into a polymer and to reveal successful approaches. The review focuses on the use of the naphthalimide‐based probes in the construction of sensing polymers. The literature overview is presented according to the nature of the guest molecules targeted for the quantitative detection: cations, anions, and small organic molecules.