Self-assembly of [2]rotaxane exploiting reversible Pt(II)- pyridine coordinate bonds

A dinuclear self-assembled cationic macrocycle based on Pt(II)-N(pyridine) coordinative bonds and having competitive triflate anions, as metal counterions, is used in the construction of [2]rotaxane and [2]pseudorotaxane architectures assisted by hydrogen bonding. The kinetic lability of the Pt(II)-N(pyridine) coordinative bond controls the dynamics of the [2]rotaxane.     

Flow injection determination of bismuth in urine by successive retention of Bi(III) and tetrahydroborate(III) on an anion-exchange resin and hydride generation atomic absorption spectrometry

Bismuth as BiCl₄⁻ and BH₄⁻ ware successively retained in a column (150 mm × 4 mm, length × i.d.) packed with Amberlite IRA-410 (strong anion-exchange resin). This was followed by passage of an injected slug of hydrochloric acid resulting in bismuthine generation (BiH₃). BiH₃ was stripped from the eluent solution by the addition of a nitrogen flow and the bulk phases were separated in a gas–liquid separator. Finally, bismutine was atomized in a quartz tube for the subsequent detection of bismuth by atomic absorption spectrometry. Different halide complexes of bismuth (namely, BiBr₄⁻, BiI₄⁻ and BiCl₄⁻) were tested for its pre-concentration, being the chloride complexes which produced the best results. Therefore, a concentration of 0.3 mol l⁻¹ of HCl was added to the samples and calibration solutions. A linear response was obtained between the detection limit (3σ) of 0.225 and 80 μg l⁻¹. The R.S.D.% (n = 10) for a solution containing 50 μg l⁻¹ of Bi was 0.85%. The tolerance of the system to interferences was evaluated by investigating the effect of the following ions: Cu²⁺, Co²⁺, Ni²⁺, Fe³⁺, Cd²⁺, Pb²⁺, Hg²⁺, Zn²⁺, and Mg²⁺. The most severe depression was caused by Hg²⁺, which at 60 mg l⁻¹ caused a 5% depression on the signal. For the other cations, concentrations between 1000 and 10,000 mg l⁻¹ could be tolerated. The system was applied to the determination of Bi in urine of patients under therapy with bismuth subcitrate. The recovery of spikes of 5 and 50 μg l⁻¹ of Bi added to the samples prior to digestion with HNO₃ and H₂O₂ was in satisfactory ranges from 95.0 to 101.0%. The concentrations of bismuth found in six selected samples using this procedure were in good agreement with those obtained by an alternative technique (ETAAS). Finally, the concentration of Bi determined in urine before and after 3 days of treatment were 1.94 ± 1.26 and 9.02 ± 5.82 μg l⁻¹, respectively.     

2-Mercaptomethyl-thiazolidines use conserved aromatic–S interactions to achieve broad-range inhibition of metallo-β-lactamases

Infections caused by multidrug resistant (MDR) bacteria are a major public health threat. Carbapenems are among the most potent antimicrobial agents that are commercially available to treat MDR bacteria. Bacterial production of carbapenem-hydrolysing metallo-β-lactamases (MBLs) challenges their safety and efficacy, with subclass B1 MBLs hydrolysing almost all β-lactam antibiotics. MBL inhibitors would fulfil an urgent clinical need by prolonging the lifetime of these life-saving drugs. Here we report the synthesis and activity of a series of 2-mercaptomethyl-thiazolidines (MMTZs), designed to replicate MBL interactions with reaction intermediates or hydrolysis products. MMTZs are potent competitive inhibitors of B1 MBLs in vitro (e.g., K_i = 0.44 μM vs. NDM-1). Crystal structures of MMTZ complexes reveal similar binding patterns to the most clinically important B1 MBLs (NDM-1, VIM-2 and IMP-1), contrasting with previously studied thiol-based MBL inhibitors, such as bisthiazolidines (BTZs) or captopril stereoisomers, which exhibit lower, more variable potencies and multiple binding modes. MMTZ binding involves thiol coordination to the Zn(ii) site and extensive hydrophobic interactions, burying the inhibitor more deeply within the active site than d/l-captopril. Unexpectedly, MMTZ binding features a thioether–π interaction with a conserved active-site aromatic residue, consistent with their equipotent inhibition and similar binding to multiple MBLs. MMTZs penetrate multiple Enterobacterales, inhibit NDM-1 in situ, and restore carbapenem potency against clinical isolates expressing B1 MBLs. Based on their inhibitory profile and lack of eukaryotic cell toxicity, MMTZs represent a promising scaffold for MBL inhibitor development. These results also suggest sulphur–π interactions can be exploited for general ligand design in medicinal chemistry.

Metallo-β-lactamases (MBLs) are major culprits of resistance to carbapenems in bacteria. A series of thiazolidines are potent MBL inhibitors, restoring the activity of carbapenems. Metal binding and sulphur–π interactions are key to inhibition.     

Nickel(II) and copper(II) – l-cysteine,l-methionine,l-tryptophan-nucleotide ternary complexes

Four new ternary complexes of Cu^II with l-methionine and the nucleotides 5AMP (adenosine 5-phosphate), 5GMP (guanosine 5-phosphate) and 5IMP (inosine 5-phosphate), and with l-tryptophan and 5AMP, were synthesized and characterized by elemental analysis and i.r. spectroscopy. One ternary complex of N^II with l-cysteine and 5IMP was also prepared and characterized. The study of the three ternary compounds of Cu^II, of general formulae Cu-5NMP-l-methionine, indicates coordination of the phosphate group and of N(7) of the purinic ring. l-Methionine is bound by the carboxylic and amino groups. The ternary complex obtained from a mixture of Cu-5AMP and l-tryptophan is a dimer in which the nucleotide bridges the two copper atoms. In the complex of Ni-5IMP and l-cysteine, the nucleotide seems to bind the metal through the N(7) of the heterocyclic ring, and the l-cysteine is coordinated as a bidentate chelate by the carboxyl and thiol groups. E.s.r. spectra of the copper complexes are in good agreement with the low symmetry structure proposed. The one-electron reduction potentials E_c(Fc⁺/Fc) (V) of Cu^II to Cu^I were established for the four copper complexes from cyclic voltammetry studies. The one-electron oxidation potential E_a(Fc⁺/Fc⁺) (V) of Ni^II to Ni^III was also measured for the nickel complex.     

Diodes as sensors in solution thermochemistry

The advantages of using diodes as thermal sensors in solution thermochemistry are discussed and a simple, low-cost circuit for the use of diodes as temperature sensors is reported. In preliminary studies, the titration of TRIS and hydrochloric acid is used to compare the precision of thermistors and diodes in thermometric titrimetry. Several systems are assayed at various temperatures by enthalpimetric methods to illustrate the advantages of diodes as sensors for monitoring thermal methods capable of being used in quality control system.     

Regularity of solutions and interfaces of a generalized porous medium equation inR N

Summary We consider the Cauchy problem for the generalized porous medium equation u_t=(u) where u=u(x, t), xRⁿ and t>0, and the initial datum u(x, 0) is assumed to be nonnegative, integrable mid to nave compact support. The nonlinearity (u) is a C¹ function defined for uO which grows like a power of u. Our assumptions generalize the porous medium case, (u)=u^m, m>1, and also include the equation of the Marshak waves. This problem has finite speed of propagation. We estimate the rate of growth of the support of the solution with precise estimates for t 0 and t. Our main result deals with the regularity of the solutions. We show that after a certain time t₀ the pressure, defined by v=(u), with (u)=(u)/u and (0)=0, is a Lipschitz-continuous function of x and t and the interface is a Lipschitz-continuous surface in R^N+1; the solution u is Hölder continuous for all times t> 0.Both authors partially supported by CAICYT, Project 2805-83. The second author also supported by USA-Spain Joint Research Grant CCB-8402023.     

Shock fluctuations in asymmetric simple exclusion

Summary The one dimensional nearest neighbors asymmetric simple exclusion process in used as a microscopic approximation to the Burgers equation. We study the process with rates of jumpsp>q to the right and left, respectively, and with initial product measure with densities < to the left and right of the origin, respectively (with shock initial conditions). We prove that a second class particle added to the system at the origin at time zero identifies microscopically the shock for all later times. If this particle is added at another site, then it describes the behavior of a characteristic of the Burgers equation. For vanishing left density (=0) we prove, in the scale t^1/2, that the position of the shock at timet depends only on the initial configuration in a region depending ont. The proofs are based on laws of large numbers for the second class particle.     

A moment problem associated to rational Szegő functions

Leta ₁,...,a _p be distinct points in the finite complex plane ?, such that |a _j|>1,j=1,..., p and let \(b_j = 1/\bar \alpha _j ,\) j=1,..., p. Let μ₀, μ _π ^(j) , ν _π ^(j) j=1,..., p;n=1, 2,... be given complex numbers. We consider the following moment problem. Find a distribution ψ on [?π, π], with infinitely many points of increase, such that $$\begin{array}{l} \int_{ - \pi }^\pi {d\psi (\theta ) = \mu _0 ,} \\ \int_{ - \pi }^\pi {\frac{{d\psi (\theta )}}{{(e^{i\theta } - a_j )^n }} = \mu _n^{(j)} ,} \int_{ - \pi }^\pi {\frac{{d\psi (\theta )}}{{(e^{i\theta } - b_j )^n }} = v_n^{(j)} ,} j = 1,...,p;n = 1,2,.... \\ \end{array}$$ It will be shown that this problem has a unique solution if the moments generate a positive-definite Hermitian inner product on the linear space of rational functions with no poles in the extended complex plane ?^* outside {a ₁,...,a _p,b ₁,...,b _p}.     

Optimal allocation of replicas in parallel tempering simulations

We have studied the efficiency of parallel tempering simulations for a variety of systems including a coarse-grained protein, an atomistic model polypeptide, and the Lennard-Jones fluid. A scheme is proposed for the optimal allocation of temperatures in these simulations. The method is compared to the existing empirical approaches used for this purpose. Accuracy associated with the computed thermodynamic quantities such as specific heat is also computed and their dependence on the trial-exchange acceptance rate is reported.     

Spectrophotometric determination of fluoride in fluoride-bearing minerals after decomposition by fusion with sodium hydroxide

The decomposition of highly insoluble minerals (fluorspar and cryolite) by fusion with molten alkali-metal hydroxides is studied. The introduction of additives such as aluminium compounds or sodium peroxide to obtain total liberation of fluoride from calcium fluoride samples, is tested. The fusion is done in a silver crucible with a Bunsen burner. The cooled melt is easily soluble, giving solutions suitable for spectrophotometric fluoride determination by the Zr(IV)-fluoride-Erichrome Cyanine R method.