Kinetic studies on the addition of dipropylamine to starch acrylate

Summary The kinetics of nucleophilic addition of dipropylamine to vinyl groups of starch acrylate has been investigated. The reactions were carried out under pseudo-first order conditions in tetrahydrofuran with excess amine within the temperature range from 25 to 45^oC. Pseudo-first-order rate constants for addition and the activation energy have been determined.     

Optimization of Aqueous Stability versus π-Conjugation in Tetracationic Bis(triarylborane) Chromophores: Applications in Live-Cell Fluorescence Imaging

The stability of tetracationic triarylboranes in dilute aqueous solution was investigated by tuning the steric demand of the linker in a (para-(N,N,N-trimethylammonio)xylyl)₂B–(linker)–B(para-(N,N,N-trimethylammonio)xylyl)₂ structure. With increasing steric bulk of the linker, namely 1,4-phenylene, 2,2′′′-(3,3′′′-dimethyl)-5,2′:5′,2′′:5′′,5′′′-quaterthiophene, 9,10-anthracenylene, and 4,4′′′-(5′-(3,5-dimethylphenyl))(5′′-(3′′′,5′′′-dimethylphenyl))-2′,2′′-bithiophene, the stability of the compounds increased. The anthracene-based chromophore, compound 3M is water-stable for at least 48 h, is nontoxic to cells and exhibits an exceedingly high fluorescence quantum yield of 0.86 in water making it an ideal candidate for confocal live-cell imaging of lysosomes.     

Improved Synthesis of Indirubin Derivatives by Sequential Build‐Up of the Indoxyl Unit: First Preparation of Fluorescent Indirubins

Indirubin, present in extracts of Isatis tinctoria and some other plant species, has promising cytotoxicity against a variety of cell lines by inhibition of cyclin‐dependent kinases. Chemical synthesis of its derivatives relies on the combination of isatins and 2,3‐dihydro‐1H‐indol‐3‐one (‘indoxyl’) derivatives and usually yields indigo as well as other by‐products. Inspection of the hydrolysis of the long‐known condensation products of 2‐thioxothiazolidin‐4‐one with isatins gave useful hints for an improved synthesis of indirubins: this reaction does not yield quinoline derivatives but 2‐(2,3‐dihydro‐2‐oxo‐1H‐indol‐3‐ylidene)‐2‐sulfanyl acetic acids. By substitution of the sulfanyl group in this oxindoles with anilines and straightforward cyclization under Nazarov conditions, a broad variety of indirubins substituted in the indoxyl ring system are thus available, usually in very good purity and yield. Use of naphthylamines in this reaction sequence yields various fluorescent substances with λ_fl at ca. 630 nm.     

Fractional Dynamics Identification via Intelligent Unpacking of the Sample Autocovariance Function by Neural Networks

Many single-particle tracking data related to the motion in crowded environments exhibit anomalous diffusion behavior. This phenomenon can be described by different theoretical models. In this paper, fractional Brownian motion (FBM) was examined as the exemplary Gaussian process with fractional dynamics. The autocovariance function (ACVF) is a function that determines completely the Gaussian process. In the case of experimental data with anomalous dynamics, the main problem is first to recognize the type of anomaly and then to reconstruct properly the physical rules governing such a phenomenon. The challenge is to identify the process from short trajectory inputs. Various approaches to address this problem can be found in the literature, e.g., theoretical properties of the sample ACVF for a given process. This method is effective; however, it does not utilize all of the information contained in the sample ACVF for a given trajectory, i.e., only values of statistics for selected lags are used for identification. An evolution of this approach is proposed in this paper, where the process is determined based on the knowledge extracted from the ACVF. The designed method is intuitive and it uses information directly available in a new fashion. Moreover, the knowledge retrieval from the sample ACVF vector is enhanced with a learning-based scheme operating on the most informative subset of available lags, which is proven to be an effective encoder of the properties inherited in complex data. Finally, the robustness of the proposed algorithm for FBM is demonstrated with the use of Monte Carlo simulations.     

Dynamic job assignment: A column generation approach with an application to surgery allocation

We consider the assignment of jobs to heterogeneous agents in a dynamic system with a rolling time horizon. An example is a hospital operating theatre where the jobs are surgeries and the agents are the surgeons. The paper is presented in the context of surgery allocation and the system is characterized as follows: Patients are grouped into categories and they arrive continually following a stochastic process. Patients in each group have specific time limits within which they need treatment and if it cannot be accommodated then the patients are outsourced. The service level is the percentage of patients in each group treated within the time limit. Surgery durations are stochastic and depend on the surgeon conducting the surgeries. Each surgeon has limited time available and expected overtime is penalized by a non-decreasing convex function. We develop a column generation approach for the assignment of already arrived patients and tentative future patients to surgeons on specific days. It balances the conflicting objectives of including as many arrived patients as possible within their time limits, maximizing the service level of future patients, and minimizing the expected overtime of surgeons. A computational study is conducted with the model embedded in a rolling time horizon frame. The study indicates that the assignment of patients based on our model increases system performance in terms of service level and reduced overtime compared to a First-Come-First-Served (FCFS) policy when the arrival rates of patients are medium to high compared to the capacity of the system.     

A New Look at Molecular and Electronic Structure of Homoleptic Diiron(II,II) Complexes with N,N-Bidentate Ligands: Combined Experimental and Theoretical Study

Paddlewheel-type binuclear complexes featuring metal−metal bonding have been the subject of widespread interest due to fundamental concern in their electronic structures and potential applications. Here, we explore the molecular and electronic structures of diiron(II,II) complexes with N,N’-diarylformamidinate ligands. While a paddlewheel-type diiron(II,II) complex with N,N’-diphenylformamidinate ligands (DPhF) exhibits the centrosymmetric [Fe₂(μ-DPhF)₄] structure, a minor alteration in the ligand system, i. e., switching from phenyl to p-tolyl N-substituted formamidinate ligand (DTolF), resulted in the isolation of an unprecedented non-centrosymmetric [Fe(μ-DTolF)₃Fe(κ²-DTolF)] complex. Both complexes were characterized using single-crystal X-ray diffraction, magnetic measurements, ⁵⁷Fe Mössbauer spectroscopy, and cyclic voltammetry along with high-level ab-initio calculations. The results provide a new view on a range of factors controlling the ground-state electronic configuration and structural diversity of homoleptic diiron(II,II) complexes. Model calculations determined that the Mayer bond orders for Fe−Fe interactions are significantly lower than 1 and equal to 0.15 and 0.28 for [Fe₂(μ-DPhF)₄] and [Fe(μ-DTolF)₃Fe(κ²-DTolF)], respectively.     

The Role of Hydrogen Bonds and Electrostatic Interactions in Enhancing Two-Photon Absorption in Green and Yellow Fluorescent Proteins

The spectral properties of fluorescent proteins (FPs) depend on the protein environment of the chromophore (CRO). A deeper understanding of the CRO – environment interactions in terms of FPs’ spectral characteristics will allow for a rational design of novel markers with desired properties. Here, we are taking a step towards achieving this important goal. With the time-dependent density functional theory (TDDFT), we calculate one- and two-photon absorption (OPA and TPA) spectra for 5 green FPs (GFPs) and 3 yellow FPs (YFPs) differing in amino acid sequence. The goal is to reveal the roles of: (i) electrostatic interactions, (ii) hydrogen-bonds (h-bonds) and (iii) h-bonds together with distant electrostatic field in absorption spectra tuning. Our results point to design hypothesis towards FPs optimised for TPA-based applications. Both h-bonds and electrostatic interactions co-operate in enhancing TPA cross-section ( ) for the transition in GFPs. Furthermore, it seems that details of h-bonds network in the CRO's vicinity influences response to CRO – environment electrostatic interactions in YFPs. We postulate that engineering FPs with more hydrophilic CRO's environment can lead to greater . We also find that removing h-bonds formed with the CRO's phenolate leads to TPA enhancement for transition to higher excited states than S₁. Particularly Y145 and T203 residues are important in this regard.