The collision induced loss of carbon monoxide from deprotonated benzyl benzoate in the gas phase. An anionic 1,2-Wittig type rearrangement

The ion PhCO2--CHPh, upon collision activation, undergoes competitive losses of CO and CO2 of which the former process produces the base peak of the spectrum. Product ion and substituent effect (Hammett) studies indicate that PhCO2--CHPh cyclises to a deprotonated hydroxydiphenyloxirane which ring opens to PhCOCH(O-)Ph. This anion then undergoes an anionic 1,2-Wittig type rearrangement {through [PhCO- (PhCHO)]} to form Ph2CHO- and CO. The mechanism of the 1,2-rearrangement has been probed by an ab initio study [at MP4(SDTQ)/6-31++G(d,p) level] of the model system HCOCH2O- →; MeO- + CO The analogous system RCO2--CHPh (R = alkyl) similarly loses CO, and the migratory aptitudes of the alkyl R groups in this reaction are Bu′ > Me > Et ∼Pri). This trend correlates with the order of anion basicities (i.e. the order of ΔG○acid values of RH), supporting the operation of an anion migration process. The loss of CO2 from PhCO2--CHPh yields Ph2CH- as the anionic product: several mechanistic scenarios are possible, one of which involves an initial ipso nucleophilic substitution.

Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

Reactions of the hydroperoxide anion with dimethyl methylphosphonate in an ion trap mass spectrometer : evidence for a gas phase alpha-effect

The gas phase degradation reactions of the chemical warfare agent (CWA) simulant, dimethyl methylphosphonate (DMMP), with the hydroperoxide anion (HOO(-)) were investigated using a modified quadrupole ion trap mass spectrometer. The HOO(-) anion reacts readily with neutral DMMP forming two significant product ions at m/z 109 and m/z 123. The major reaction pathways correspond to (i) the nucleophilic substitution at carbon to form \[CH(3)P(O)(OCH(3))O](-) (m/z 109) in a highly exothermic process and (ii) exothermic proton transfer. The branching ratios of the two reaction pathways, 89% and 11% respectively, indicate that the former reaction is significantly faster than the latter. This is in contrast to the trend for the methoxide anion with DMMP, where proton transfer dominates. The difference in the observed reactivities of the HOO(-) and CH(3)O(-) anions can be considered as evidence for an a-effect in the gas phase and is supported by electronic structure calculations at the B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory that indicate the S(N)2(carbon) process has an activation energy 7.8 kJ mol(-1) lower for HOO(-) as compared to CH(3)O(-). A similar alpha-effect was calculated for nucleophilic addition-elimination at phosphorus, but this process an important step in the perhydrolysis degradation of CWAs in solution - was not observed to occur with DMMP in the gas phase. A theoretical investigation revealed that all processes are energetically accessible with negative activation energies. However, comparison of the relative Arrhenius pre-exponential factors indicate that substitution at phosphorus is not kinetically competitive with respect to the S(N)2(carbon) and deprotonation processes.

Ion-molecule reactions of O,S-Dimethyl methylphosphonothioate : Evidence for intramolecular sulfur oxidation during VX perhydrolysis

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous Solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

Crisis on impact : responding to cyber attacks on critical information infrastructures

In the developing digital economy, the notion of traditional attack on enterprises of national significance or interest has transcended into different modes of electronic attack, surpassing accepted traditional forms of physical attack upon a target. The terrorist attacks that took place in the United States on September 11, 2001 demonstrated the physical devastation that could occur if any nation were the target of a large-scale terrorist attack. Therefore, there is a need to protect criticalnational infrastructure and critical information infrastructure. In particular,this protection is crucial for the proper functioning of a modern society and for a government to fulfill one of its most important prerogatives – namely, the protection of its people. Computer networks have many benefits that governments, corporations, and individuals alike take advantage of in order to promote and perform their duties and roles. Today, there is almost complete dependence on private sector telecommunication infrastructures and the associated computer hardware and software systems.1 These infrastructures and systems even support government and defense activity.2 This Article discusses possible attacks on critical information infrastructures and the government reactions to these attacks.

Hydrolysis of triasulfuron, metsulfuron-methyl and chlorsulfuron in alkaline soil and aqueous solutions

The hydrolysis of triasulfuron, metsulfuron-methyl and chlorsulfuron in aqueous buffer solutions and in soil suspensions at pH values ranging from 5.2 to 11.2 was investigated. Hydrolysis of all three compounds in both aqueous buffer and soil suspensions was highly pH-sensitive. The rate of hydrolysis was much faster in the acidic pH range (5.2-6.2) than under neutral and moderately alkaline conditions (8.2-9.4), but it increased rapidly as the pH exceeded 10.2. All three compounds degraded faster at pH 5.2 than at pH 11.2. Hydrolysis rates of all three compounds could be described well with pseudo-first-order kinetics. There were no significant differences (P =0.05) in the rate constants (k, day-1) of the three compounds in soil suspensions from those in buffer solutions within the pH ranges studied. A functional relationship based on the propensity of nonionic and anionic species of the herbicides to hydrolyse was used to describe the dependence of the 'rate constant' on pH. The hydrolysis involving attack by neutral water was at least 100-fold faster when the sulfonylurea herbicides were undissociated (acidic conditions) than when they were present as the anion at near neutral pH. In aqueous buffer solution at pH > 11, a prominent degradation pathway involved O-demethylation of metsulfuron-methyl to yield a highly polar degradate, and hydrolytic opening of the triazine ring. It is concluded that these herbicides are not likely to degrade substantially through hydrolysis in most agricultural (C) 2000 Society of Chemical Industry.

Security analysis of the non-aggressive challenge response of the DNP3 Protocol using a CPN Model

Distributed Network Protocol Version 3 (DNP3) is the de-facto communication protocol for power grids. Standard-based interoperability among devices has made the protocol useful to other infrastructures such as water, sewage, oil and gas. DNP3 is designed to facilitate interaction between master stations and outstations. In this paper, we apply a formal modelling methodology called Coloured Petri Nets (CPN) to create an executable model representation of DNP3 protocol. The model facilitates the analysis of the protocol to ensure that the protocol will behave as expected. Also, we illustrate how to verify and validate the behaviour of the protocol, using the CPN model and the corresponding state space tool to determine if there are insecure states. With this approach, we were able to identify a Denial of Service (DoS) attack against the DNP3 protocol.

Root caries patterns and risk factors of middle-aged and elderly people in China

The objectives of this study were to describe root caries patterns of Chinese adults and to analyze the effect of selected demographic and socioeconomic factors on these patterns. A total sample of 1080 residents aged 35-44-years-old and 1080 residents aged 65-74-years-old from three urban and three rural survey sites in Hubei Province participated in both an oral health interview and a clinical oral health examination. Root surface caries prevalence rates were 13.1% in the middle-aged group and 43.9% in the elderly group. The mean number of teeth affected by caries in the middle-aged group was reported at 0.21 and 1.0 in the elderly group. Mean Root Caries Index (RCI) scores of the middle-aged were reported at 6.29 and elderly subjects were reported at 11.95. Elderly people living in rural areas reported a higher RCI score (13.24) than those living in urban areas (10.70). A significantly higher frequency of root surface caries was observed in elderly participants (P < 0.001, OR = 3.80) and ethnic minorities (P < 0.001, OR = 1.93). In addition, smokers, nontea drinkers, and those with an annual household income of 10,000 yuan or less tended to have higher caries prevalence. RCI figures for the different tooth types ranged from 1% to 16%, indicating a wide variation in attack rates. In conclusion, our study suggests that root surface caries occurrence is high among the Chinese adult population, especially older adults. With an increasing number of retained teeth in both middle-aged and elderly people, root caries is a growing disease in the People's Republic of China which deserves more attention in future research.

Algebraic attacks on SOBER-t32 and SOBER-t16 without stuttering

This paper presents algebraic attacks on SOBER-t32 and SOBER-t16 without stuttering. For unstuttered SOBER-t32, two different attacks are implemented. In the first attack, we obtain multivariate equations of degree 10. Then, an algebraic attack is developed using a collection of output bits whose relation to the initial state of the LFSR can be described by low-degree equations. The resulting system of equations contains 2^69 equations and monomials, which can be solved using the Gaussian elimination with the complexity of 2^196.5. For the second attack, we build a multivariate equation of degree 14. We focus on the property of the equation that the monomials which are combined with output bit are linear. By applying the Berlekamp-Massey algorithm, we can obtain a system of linear equations and the initial states of the LFSR can be recovered. The complexity of attack is around O(2^100) with 2^92 keystream observations. The second algebraic attack is applicable to SOBER-t16 without stuttering. The attack takes around O(2^85) CPU clocks with 2^78 keystream observations.

Cheating prevention in linear secret sharing

Cheating detection in linear secret sharing is considered. The model of cheating extends the Tompa-Woll attack and includes cheating during multiple (unsuccessful) recovery of the secret. It is shown that shares in most linear schemes can be split into subshares. Subshares can be used by participants to trade perfectness of the scheme with cheating prevention. Evaluation of cheating prevention is given in the context of different strategies applied by cheaters.

Finding good differential patterns for attacks on SHA-1

In this paper we analyse properties of the message expansion algorithm of SHA-1 and describe a method of finding differential patterns that may be used to attack reduced versions of SHA-1. We show that the problem of finding optimal differential patterns for SHA-1 is equivalent to the problem of finding minimal weight codeword in a large linear code. Finally, we present a number of patterns of different lengths suitable for finding collisions and near-collisions and discuss some bounds on minimal weights of them.

Cryptanalysis of block ciphers with overdefined systems of equations

Several recently proposed ciphers, for example Rijndael and Serpent, are built with layers of small S-boxes interconnected by linear key-dependent layers. Their security relies on the fact, that the classical methods of cryptanalysis (e.g. linear or differential attacks) are based on probabilistic characteristics, which makes their security grow exponentially with the number of rounds N r r. In this paper we study the security of such ciphers under an additional hypothesis: the S-box can be described by an overdefined system of algebraic equations (true with probability 1). We show that this is true for both Serpent (due to a small size of S-boxes) and Rijndael (due to unexpected algebraic properties). We study general methods known for solving overdefined systems of equations, such as XL from Eurocrypt’00, and show their inefficiency. Then we introduce a new method called XSL that uses the sparsity of the equations and their specific structure. The XSL attack uses only relations true with probability 1, and thus the security does not have to grow exponentially in the number of rounds. XSL has a parameter P, and from our estimations is seems that P should be a constant or grow very slowly with the number of rounds. The XSL attack would then be polynomial (or subexponential) in N r> , with a huge constant that is double-exponential in the size of the S-box. The exact complexity of such attacks is not known due to the redundant equations. Though the presented version of the XSL attack always gives always more than the exhaustive search for Rijndael, it seems to (marginally) break 256-bit Serpent. We suggest a new criterion for design of S-boxes in block ciphers: they should not be describable by a system of polynomial equations that is too small or too overdefined.

Cryptanalysis of FORK-256

In this paper we present a cryptanalysis of a new 256-bit hash function, FORK-256, proposed by Hong et al. at FSE 2006. This cryptanalysis is based on some unexpected differentials existing for the step transformation. We show their possible uses in different attack scenarios by giving a 1-bit (resp. 2-bit) near collision attack against the full compression function of FORK-256 running with complexity of 2^125 (resp. 2^120) and with negligible memory, and by exhibiting a 22-bit near pseudo-collision. We also show that we can find collisions for the full compression function with a small amount of memory with complexity not exceeding 2^126.6 hash evaluations. We further show how to reduce this complexity to 2^109.6 hash computations by using 273 memory words. Finally, we show that this attack can be extended with no additional cost to find collisions for the full hash function, i.e. with the predefined IV.

Social engineering in social networking sites : how good becomes evil

Social Engineering (ES) is now considered the great security threat to people and organizations. Ever since the existence of human beings, fraudulent and deceptive people have used social engineering tricks and tactics to trick victims into obeying them. There are a number of social engineering techniques that are used in information technology to compromise security defences and attack people or organizations such as phishing, identity theft, spamming, impersonation, and spaying. Recently, researchers have suggested that social networking sites (SNSs) are the most common source and best breeding grounds for exploiting the vulnerabilities of people and launching a variety of social engineering based attacks. However, the literature shows a lack of information about what types of social engineering threats exist on SNSs. This study is part of a project that attempts to predict a persons’ vulnerability to SE based on demographic factors. In this paper, we demonstrate the different types of social engineering based attacks that exist on SNSs, the purposes of these attacks, reasons why people fell (or did not fall) for these attacks, based on users’ opinions. A qualitative questionnaire-based survey was conducted to collect and analyse people’s experiences with social engineering tricks, deceptions, or attacks on SNSs.

Cryptology and network security

This book constitutes the refereed proceedings of the 11th International Conference on Cryptology and Network Security, CANS 2012, held in Darmstadt, Germany, in December 2012. The 22 revised full papers, presented were carefully reviewed and selected from 99 submissions. The papers are organized in topical sections on cryptanalysis; network security; cryptographic protocols; encryption; and s-box theory.